GLP10-01-01. Interim Report 27: Analysis of PFOA in Surface Water Samples Collected at 

Bert Jeffries Landfill in Decatur. AL in February 2012 

Study Title 

Analysis of Perfluorooctanoic Acid (PFOA) in Groundwater, Soil and Sediment for the 3M Decatur Phase 3 

Site-Related Monitoring Program 

Data Requirement 

EPA TSCA Good Laboratory Practice Standards 40 CFR Part 792 

Study Director 

Jaisimha Kesari P.E., DEE 

Weston Solutions, Inc. 

1400 Weston Way 

West Chester, PA 19380 

Phone:610-701-3761 

Author 

Susan Wolf 

3M Environmental Laboratory 

Interim Report Completion Date 

Date of signing 

Performing Laboratory 

3M Environmental Health and Safety Operations 

Environmental Laboratory 

3M Center, BIdg 260-05-N-17 

St. Paul, MN 55144 

Project Identification 

GLPlO-01-01-27 

Total Number of Pages 

61 

^CTTT^— \ The testing reported herein meet the requirements of ANSI/ISO/lEC 17025:2005 "General 

^^m j 1 Requirements for the Competence of Testing and Calibration Laboratories", in accordance with 

^^V ^ ^^ ^ / the A2LA Testing Certificate # 2052.01. Testing that complies with this Intemational Standard 

i7rT'>'-=-3 also meets principles of ISO 9001:2000. IACCREPITEPI 

Testing Cert #2052.01 
This page has been reserved for specific country requirements. 

Page 2 of 61 
GLP10-01-01; Interim Report 27 

Analysis of PFOA in Surface Water 

Bert Jeffries Landfill - February 2012 

GLP COMPLIANCE STATEMENT 

Report Title: GLPl0-01-01, Interim Report 27. Analysis of PFOA in Surface Water Samples Collected 

at Bert Jeffries Landfill in Decatur, AL in February 2012 

Study: Analysis of Perfluorooctanoic Acid (PFOA) in Groundwater, Soil and Sediment for the 3M 

Decatur Phase 3 Site-Related Monitoring Program. 

This analytical phase was conducted in compliance with Toxic Substances Control Act (TSCA) Good 

Laboratory Practice (GLP) Standards, 40 CFR 792, with the exceptions listed below: 

• These are environmental samples where there is no specific test substance, no specific test 

system and no dosing of a test system. 

• The reference substances have not been characterized under the GLPs and the stability under 

storage conditions at the test site have not been determined under GLPs. 

Gary Hohenstein, Sponsor Representative Date 

1 

Jaisimha Kesari.'P.E., DEE, Study Director ' Date 

Page 3 of 61 
GLP10-01-01; Interim Report 27 

Analysis of PFOA in Surface Water 

Bert Jeffries Landfill - February 2012 

QUALITY ASSURANCE STATEMENT 

Report Title: GLP10-01-01, Interim Report 27. Analysis of PFOA in Surface Water Samples Collected 

at Bert Jeffries Landfill in Decatur, AL in February 2012 

Study: Analysis of Perfluorooctanoic Acid (PFOA) in Groundwater, Soil and Sediment for the 3M 

Decatur Phase 3 Site-Related Monitoring Program. 

This report and the accompanying data were audited by the 3M Environmental Laboratory Quality 

Assurance Unit (QAU), as indicated below. The findings were reported to the principal analytical 

investigator (P.A.I.), laboratory management and study director. 

Date Reported to 

Inspection Dates Phase Testing Facility Study Director 

Management 

Study Director 

3/30/12 and 4/2/12 Data and Report 4/9/12 4/6/12 

QAU Repres^itativ c e Date 

Page 4 of 61 
TABLE OF CONTENTS 

GLP Compliance Statement 3 

Quality Assurance Statement 4 

Table of Contents 5 

List of Tables 6 

1 Study infomiation 7 

2 Summary 8 

3 Introduction.... 9 

4 Test & Control Substances 9 

5 Reference Substances 10 

6 Test System 10 

7 Method Summary 1 

7.1 Methods : 1 

7.2 Sample Collection 1 

7.3 Sam pie Preparation 1 

7.4 Analysis 1 

8 Analytical Results 12 

8.1 Calibration 12 

8.2 System Suitability 12 

8.3 Limit of Quantitation (LOQ) 13 

8.4 Continuing Calibration 13 

8.5 Blanks 13 

8.6 Lab Control Spikes (LCSs) 13 

8.7 /Analytical Method Uncertainty 14 

8.8 Field Matrix Spikes (FMS) 14 

Page 5 of 61 
9 Data Summary and Discussion 15 

10 Conclusion 18 

11 Data/Sample Retention 18 

12 Attachments 18 

13 Signatures 19 

LIST OF TABLES 

Table 1. Summarized PFOA Results (Jeffries Landfill Site, February 2012) 8 

Table 2. Sample Description Key Code 10 

Table 3. Instrument Parameters 11 

Table 4. Liquid Chromatography Conditions 12 

Table 5. Mass Transitions 12 

Table 6. Limit of Quantitation (LOQ) 13 

Table 7. Laboratory Control Spike Recovery 14 

Tables. Analytical Method Uncertainty 14 

Table 9. Field Matrix Spike Levels 15 

Table 10. JPAL SW ET01 120228 16 

Table 11. JPAL SW ET02 120228 16 

Table 12. JPAL SW ET03 120228 16 

Table 13. JPAL SW ET04 120228 17 

Table 14. Trip Blank 120228 17 

Page 6 of 61 
1 study Information 

Sponsor 

3M Company 

Sponsor Representative 

Gary Hohenstein 

3M EHS Operations 

3M Building 224-5W-03 

Saint Paul, MN 55144-1000 

Phone:(651)737-3570 

Study Director 

Jaisimha Kesari, P.E., DEE 

Weston Solutions, Inc. 

Westchester, PA 19380 

Phone: (610)701-3761 

Fax: (610) 701-7401 

j.kesari@westonsolutions.com 

Study Location 

Testing Facility 

3M EHS Operations 

3M Environmental Laboratory 

Building 260-5N-17 

St. Paul, MN 55144 

Study Personnel 

William K. Reagen, Ph.D., 3M Laboratory Manager 

Cleston Lange, Ph.D., Principal /Analytical Investigator. (clanqe(5)mmm.com): phone (651)-733-9860 

Susan Wolf, 3M Analyst 

Chelsie Grochow, Analyst 

Kevin Eich, Analyst 

Kelly Ukes, Analyst 

Jonathan Steege, Analyst 

Study Dates 

Study Initiation: March 8,2010 

Interim Report 27 Experimental Tennination: March 7,2012 

Interim Report Completion: Date of Interim Report Signing 

Location of Archives 

All original raw data and the analytical report have been archived at the 3M Environmental 

Laboratory according to 40 CFR Part 792. The test substance and analytical reference standard 

reserve samples are archived at the 3M Environmental Laboratory according to 40 CFR Part 792 

Page 7 of 61 
2 Summary 

The 3M Environmental Laboratory received surface water samples from four different locations located 

at Jeffries Landfill in Decatur, AL. A total of nineteen sample bottles were received at the 3M 

Environmental Laboratory for perfluorooctanoate (PFOA) analysis and included duplicate surface water 

samples and two field matrix spike (FMS) samples from each sampling location. A set of trip blank 

samples; single trip blank containing Milli-QTM water and two trip blank spikes, were included with the 

sample bottles. /\11 samples were logged into the laboratory information management system (LIMS) 

under project GLPlO-01-01-27. The surface water samples and trip blanks were received from Weston 

personnel on March 2, 2012. Ai\ of the samples were prepared and analyzed for PFOA and the 

sun^ogate recovery standard ^^C4-PF0A, following 3M Environmental Laboratory Method ETS-8-044.1. 

The average measured PFOA concentrations are summarized in Table 1. The trip blank was below 

the lower limit of quantitation (LLOQ) of 0.0240 ng/mL, indicating adequate control of sample 

contamination during shipping and sample collection. The analytical uncertainty was estimated at 

100±17%. 

Table 1. Summarized PFOA Results (Jeffries Landfill Site, February 2012) 

3M LIMS ID Sample Description 

PFOA 

Concentration 

(ng/mL) 

GLPl 0-01-01-027-005 JP/M.-SW-ET01 -0-120228 <0.0240 

GLPl 0-01-01-027-006 JPAL-SW-ET01 -DB-120228 <0.0240 

Average <0.0240 

VoRPD Sample/Sample Dup NA 

GLPl 0-01-01-027-009 JPAL-SW-ET02-0-120228 <0.0240 

GLPl 0-01-01-027-010 JPAL-SW-ET02-DB-120228 <0.0240 

Average <0.0240 

%RPD Sample/Sample Dup NA 

GLPl 0-01-01-027-013 JPAL-SW-ET03-0-120228 0.114 

GLPl 0-01-01-027-014 JPAL-SW-ET03-DB-120228 0.110 

Average 0.112 

%RPD Sample/Sarrtple Dup 3.6 

GLPl 0-01-01-027-017 JP/M.-SW-ET04-0-120228 0.0644 

GLPl 0-01-01-027-018 JPAL-SW-ET04-DB-120228 0.0709 

Av^erage 0.0677 

%RPD Sample/Sample Dup 9.6 

GLPl 0-01-01-027-025 JPAL-SW-TRIP1-0-120228 <0.0240 

NA = Not Applicable 

The analytical method uncertainty for PFOA is +17%. 

Page 8 of 61 
3 Introduction 

This analytical study was conducted as part of the Phase 3 Environmental Monitoring and Assessment 

Program for the 3M facility located in Decatur, Alabama. The objective of the overall program is to gain 

infomnation regarding concentrations of perfluorooctanoate (PFOA) in various environmental media 

such as groundwater, soils and sediments that are associated with and near the Decatur facility. This 

analytical study was conducted to analyze surface water samples collected from four locations near 

Jeffries Landfill in Decatur, AL for PFOA. 

The 3M Environmental Laboratory prepared sample bottles (250 mL high-density polyethylene) which 

were shipped to Decatur, AL Weston personnel prior to field sampling. Sample bottle sets for each 

sampling location included a field sample, field sample duplicate, and two field spike samples. Each 

empty container for samplings was mari<ed with a 'iiil to here" line to produce a final sample volume of 

200 mL. Containers designated for field matrix samples were fortified wflth an appropriate matrix spike 

solution containing PFOA prior to being sent to the field for sample collection. M sample bottles 

included the addition of ^^Ce-PFOA (internal standard) at a nominal concentration of 1 ng/mL, and "C4-

PFOA (surrogate recovery standard) at a nominal concentration of 0.1 ng/mL. See section 8.8 of the 

report for field matrix spike levels. 

Samples were prepared and analyzed according to the procedure defined in 3M Environmental 

Laboratory method ETS-8-044.1 "Method of /Analysis for the Determination of Perfluorinated 

Compounds in Water by LC/MS/MS; Direct Injection /Analysis". The use of an internal standard was 

used to aid in the data quality objectives. 

Table 1 summarizes the average PFOA concentration for the duplicate surface water samples 

collected and the trip blank sample. Tables 10-14 summarize the individual sample results and the 

associated FMS recoveries. /All results for the quality control samples prepared and analyzed with the 

samples are reported and discussed elsewhere in this report. 

4 Test & Control Substances 

There was not a test substance or control substances in the classic sense of a GLP study. This study 

was purely analytical in nature. 

Page 9 of 61 
5 Reference Substances 

The analytical reference substances used for this study are listed below. 

Reference 

Substance 

PFOA 

(LInear+Branched) "C4-PFOA "Ce-PFOA "Ctf-PFOA 

Chemical Name Perfluorooctanoate Perfluorooctanoate Perfluorooctanoate Perfluorooctanoate 

Chemical Fotmula C7F15COOH ''C4HF15O2 ''C8HF15O2 ^^C8HFl502 

Identifier CAS #95328-99-7 MPFOA MPFC-C-0511 MPFC-C-0112 

Use 

Target /Analyte 

Reference Standard Surrogate Intemal Standard Intemal Standard 

Source Wellington Wellington Wellington Wellington 

Expiration Date 03/17/2014 12/07/2013 05/25/2014 01/24/2015 

Storage Conditions Frozen Frozen Frozen Frozen 

Chemical Lot Number TPFOA0311 MPFOA1210 052411 012312 

TCR Number 

TCR11-0009, 

TCR11-0042 

TCR11-0001 TCR11-0016 TCR12-0004 

Physical Description Liquid Liquid Liquid Liquid 

Purity 98.3% >98% NA<^> NA<^> 

(1) Compound is part of a custom mixture of mass-lak)eled perfluorinated compounds at a concentration of 5.0 \i9lmL. 

6 Test System 

There was not a test system for this study in the classic sense of a GLP study. This study was 

conducted for analysis of surface water samples collected fi-om the Jeffries property located near 

Decatur, AL by Weston Solutions, Inc. personnel. Samples for this study are "real worid" environmental 

samples. 

Table 2. Sample Description Key Code. 

string Number String Descriptor Example 

Example JPAL-SW-ET01-O-120228 

1 Sample Location JPAL= Jeffries Property, Alabama 

2 Sample Type SW= Surfyce Water 

3 Well ID Example: ET01 

ET=Eastern tributary to Mallard Creek 

4 Sampling Date 120228- February 28, 2012 

5 Sample Type 0=primary sample 

DB=dupllcate sample 

LS = low spike 

HS = high spike 

Page 10 of 61 
7 Method Summary 

7.1 Method 

/Analysis for all analytes was completed following 3M Environmental Laboratory method ETS-8-044.1 

"Method of Analysis for the Determination of Perfluorinated Compounds In Water by High Performance 

Liquid Chromatography/Mass Spectrometry Direct Injection /Analysis". 

7.2 Sample Collection 

Samples were collected in 250 mL Nalgene^^ (high-density polyethylene) bottles prepared at the 3M 

Environmental Laboratory. Sample bottles associated with GLPlO-01-01-27 were retumed to the 

laboratory at ambient conditions on March 2, 2012. Samples were stored refrigerated at the laboratory 

after receipt. A set of laboratory prepared Trip Blank and Trip Blank field matrix spikes were sent with 

the set of sample collecfion bottles. 

7.3 Sample Preparation 

Samples were prepared by removing an aliquot of the well mixed sample and placing it in an autovial for 

analysis. 

During the preparation of the laboratory control samples, an aliquot of a separate intemal standard 

spiking solution was added to the laboratory control samples (nominal concentration of 1 ng/mL). The 

samples bottles were spiked with an intemal standard mix at a nominal concentration of 1 ng/mL prior to 

being sent to the field for sample collection. 

7.4 Analysis 

All study samples and quality control samples were analyzed for PFOA using high perfomnance liquid 

chromatography/ tandem mass spectrometry (HPLC/MS/MS). Detailed instrument parameters, the 

liquid chromatography gradient program, and the specific mass transitions analyzed are described in the 

raw data hard copies placed in the final data packet, and are briefly described below in Table 3, Table 4 

and Table 5. 

Table 3. Instrument Parameters. 

Instrument Name ETS Ginger 

Analytical Method Followed ETS-8-044.1 

Analysis Date 3/6/12 

Liquid Chromatograph Agilent 1100 

Guard column Betasii C18 (4.6 mm X100 mm), 5n 

Analytical column Betasil C18 (4.6 mm X100 mm), 5u 

Injection Volume 25 nL 

Mass Spectrometer Applied Biosystems API 5000 

Ion Source Turix) Spray 

Electrode Turbo Ion electrode 

Polarity Negative 

Software Analyst 1.4.2 

Page 11 of 61 
Table 4. Liquid Chromatography Conditions. 

Step Total Time Flow Rate PercentA PercentB 

Number (min) (/JJmin) (2 mM ammonium acetate) (MethanoO 

ETS-8-044.1 Analysis 

0 0.0 750 97.0 3.0 

1 2.0 750 97.0 3.0 

2 14.5 750 5.0 95.0 

3 15.5 750 5.0 95.0 

4 16.5 750 97.0 3.0 

5 20.0 750 97.0 3.0 

Table 5. Mass Transitions. 

Analyte 

Mass Transition 

Q1/Q3 

Internal Standard Mass Transition 

Q1/Q3 

PFOA 

413/369 

413/219 ["CJ-PFOA 421/376 

413/169 

fCil-PFOA 417/372 ["CsI-PFOA 421/376 

Dwell time was 50 msec for each transition. The Individual transitions were summed to produce a 

"total ion chromatogram" (TIC), which was used for quantitation. 

8 Analytical Results 

8.1 Calibration 

Samples were analyzed using a stable isotope intemal standard calibration curve. Calibration standards 

were prepared by spiking known amounts of the stock solution containing PFOA (reference standard 

containing both linear and branched isomers) into a laboratory-prepared synthefic groundwater 

containing calcium and magnesium. A separate intemal standard spiking solution was prepared and an 

aliquot was added at the same level to all calibration standards and laboratory control samples at a 

nominal concentration of 1 ng/mL. A calibration curve ranging from approximately 0.025 ng/mL to 100 

ng/mL (0.025 ng/mL to 10 ng/mL for ^^C4-PF0A surrogate) was prepared. A quadratic, 1/x weighted, 

calibration curve of the standard peak area/peak area ratios was used to fit the data for each analyte. 

The data were not forced through zero during the fitting process. Calculating the standard 

concentrations using the peak area/ peak area ratios and the resultant calibration curve confimied 

accuracy of each curve point. 

Each curve point was quantitated using the overall calibration curve and reviewed for accuracy. Method 

calibration accuracy requirements of 100 ± 25% (100 ± 30% for the lowest curve point) were met for 

PFOA and 

analytes. 

13, C4-PFOA surrogate. The correlation coefficient (r) was greater than 0.995 for both 

8.2 System Suitability 

A calibration standard was analyzed four times at the beginning of the analytical sequence to 

demonstrate overall system suitability. The acceptance criteria of less than or equal to 5% relative 

standard deviation (RSD) for peak area and retention time criteria of less than or equal to 2% RSD was 

met for PFOA and C4-PFOA sun-ogate. 

Page 12 of 61 
GLP10-01-01; interim Report 27 

Analysis of PFOA in Surface Water 

Bert Jeffries Landflii - February 2012 

8.3 Limit of Quantitation (LOQ) 

The LOQ for this analysis is the lowest non-zero calibration standard in the curve that meets linearity 

and accuracy requirements and for which the area counts are at least twice those of the appropriate 

blanks. The nominal LOQ for PFOA can be found in Table 6. 

Table 6. Limit of Quantitation (LOQ). 

Analysis Date PFOA 

ng/mL 

3/6/12 0.0240 

8.4 Continuing Calibration 

During the course of each analytical sequence, continuing calibration verification samples (CC\/s) were 

analyzed to confirm that the instrument response and the initial calibration curve were still in control. All 

CCVs met method criteria of 100% ± 25% for PFOA and "C4-PFOA surrogate. 

8.5 Blanks 

Two types of blanks were prepared and analyzed with the samples: procedural blanks and trip blanks. 

Procedural blank results were reviewed and used to evaluate method performance to detennine the 

LOQ. Trip blanks refiect the shipping and sample collection conditons the sample bottles and samples 

experience. 

8.6 Lab Control Spikes (LCSs) 

Low, mid, and high lab control spikes were prepared for the target analytes and analyzed in triplicate, 

while only low and high lab control spikes were prepared for the "C4-PFOA surrogate. LCSs were 

prepared by spiking known amounts of the analyte into 10 mL of synthetic groundwater to produce the 

desired concentration. The spiked water samples were then analyzed in the same manner as the 

samples. The method acceptance criteria, average of LCS at each level should be within 100% ± 20% 

with an RSD <20%, were met for both PFOA and "C4-PFOA surrogate. 

The following calculations were used to generate data in Table 7 for laboratory control spikes: 

, n . „ Calculated Concentration,.,.,.„, 

LCS Percent Recovery = 100% 

Spike Concentration 

LCS% RSD = "^^"^^^^ ^^P'"^^*^" M00% 

average LCS recovery 

Page 13 of 61 
Table 7. Laboratory Control Spike Recovery. 

ETS-8-044.1 

Analyzed 3/6/12 PFOA (Linear + Branched) "C4-PFOA surrogate 

Spiked 

Concentration 

Calculated 

Concentration 

Spiked 

Concentration 

Calculated 

Concentration 

Lab ID (ng/mL) (ng/mL) VoRecovery (ng/mL) (ng/mL) %Recovery 

LCS-120306-1 0.190 0.162 85.5 0.198 0.229 116 

LCS-120306-2 0.190 0.166 87.6 0.198 0.223 112 

LCS-120306-3 0.190 0.164 86.1 0.198 0.219 110 

Average ± %RSD 86.4% ±1.3% 113% ±2.7% 

LCS-120306^ 1.90 1.88 99.1 1.98 2.24 113 

LCS-120306-5 1.90 1.96 103 1.98 2.31 116 

LCS-120306-6 1.90 1.86 97.9 1.98 2.33 118 

Average ± %RSD 100% ±2.7% 116% ±2.2% 

LCS-120306-7 19.0 18.0 95.0 NA NA NA 

LCS-120306-8 19.0 17.8 93.8 NA NA NA 

LCS-120306-9 19.0 16.9 89.1 NA NA NA 

Average ± %RSD 92.6% ±3.4% NA 

NA = Not Applicable 

8.7 Analytical Method Uncertainty 

/Analytical uncertainty is based on historical QC data that is control charted and used to evaluate 

method accuracy and precision. The method uncertainty is calculated following ETS-12-012.2. The 

standard deviation is calculated for the set of accuracy results (in %) obtained for the QC samples. The 

expanded uncertainty is calculated by multiplying the standard deviation by a factor of 2, which 

con-esponds to a confidence level of 95%. 

Table 8. Analytical Method Uncertainty. 

Analyte Method Standard Deviation Method 

Uncertainty 

PFOA ETS-8-044.1 8.68 ±17% 

8.8 Field IVIatrix Spikes (FMS) 

Low and high field matrix spikes were collected at each sampling point to verify that the analytical 

method is applicable to the collected matrix. Field matrix spikes were generated by adding a measured 

volume of field sample to a container spiked by the laboratory with PFOA (reference standard containing 

both linear and branched isomers) prior to shipping sample containers for sample collection. Field 

matrix spike recoveries witiiin method acceptance criteria of 100±30% confimn that "unknown" 

components in the sample matrix do not significantiy interfere with the extraction and analysis of the 

analytes of interest. Field matrix spike concentrations must be 50% of the sample concentration to be 

considered an appropriate field spike. Field matrix spikes are presented in section 9 of this report. 

Page 14 of 61 
GLPl 0-01-01; interim Report 27 

Analysis of PFOA in Surface Water 

Bert Jeffries Landfill - February 2012 

Table 9. Field Matrix Spike Levels. 

Sampling Location Spike Level PFOA, ng/mL 

All Locations and Trip Blank 

Low 0998 All Locations and Trip Blank High 9.98 

FMSRecove _( Sample Concentration of FMS - Average Concentration: Field Sample & Field Sample Dup.), ^QQ^ 

Spike Concentraton 

8.9 Data Summary and Discussion 

The tables below summarize the sample results and field matrix spike recoveries for the sampling 

locations as well as the Trip Blanks. Results and average values are rounded to three significant 

figures according to EPA rounding rules. Because of rounding, values may vary slightly from those 

listed in the raw data. Field matrix spike recoveries meeting the method acceptance criteria of ± 30%, 

demonstrate that the method was appropriate for the given matrix and their respective quantitative 

ranges. 

Page 15 of 61 
Table 10. JPALSWET01 120228 

PFOA "C4PFOA 

Concentration 

3M LIMS ID Description (ng/mL) VoRecovery VoRecovery 

GLPl 0-01-01-27-005 J PAL-SW-ET01-0-120228 <0.0240 NA 111 

GLPl 0-01-01-27-006 J PAL-SW-ET01 -DB-120228 <0.0240 NA 108 

GLPl 0-01-01-27-007 JPAL-SW-ET01-LS-120228 0.950 95.2 110 

GLPl 0-01-01-27-008 J PAL-SW-ET01 -HS-120228 9.44 94.6 118 

Average Concentration (ng/mL) ± %RPD/RSD <0.0240 ng/mL 112%±3.9°/o 

NA = Not Applicable 

Table 11. JPAL SW ET02 120228 

PFOA "C4PFOA 

Concentration 

3M LIMS ID Description (ng/mL) VoRecovery VoRecovery 

GLPl 0-01-01-27-009 JPAL-SW-ET02-0-120228 <0.0240 NA 109 

GLPl 0-01-01-27-010 JPAL-SW-ET02-DB-120228 <0.0240 NA 115 

GLPl 0-01-01-27-011 JPAL-SW-ET02-LS-120228 0.938 94.0 106 

GLP10-01-01-27-012 JPAL-SW-ET02-HS-120228 9.02 90.4 111 

Average Concentration (ng/mL) ± VoRPD/RSD <0.0240 ng/mL 110% ±3.4% 

NA = Not Applicable 

Table 12. JPAL SW ET03 120228 

PFOA "C4PFOA 

Concentration 

3M LIMS ID Description (ng/mL) VoRecovery VoRecovery 

GLPl 0-01-01-27-013 JPAL-SW-ET03-0-120228 0.114 NA 107 

GLP10-01-01-27-014 J PAL-SW-ET03-DB-120228 0.110 NA 108 

GLP10-01-01-27-015 JPAL-SW-ET03-LS-120228 1.10 99.0 110 

GLP10-01-01-27-016 J PAL-SW-ET03-HS-120228 9.37 92.8 110 

Average Concentration (ng/mL) ± VoRPD/RSD 0.112 ng/mL ±3.6% 109% ± 1.4% 

NA = Not Applicable 

Page 16 of 61 
Table 13. JPAL SW ET04 120228 

PFOA "C4PFOA 

Concentration 

3M LIMS ID Description (ng/mL) VoRecovery VoRecovery 

GLP10-01-01-27-017 JPAL-SW-ET04-0-120228 0.0644 NA 112 

GLP10-01-01-27-018 JPAL-SW-ET04-DB-120228 0.0709 NA 111 

GLPl 0-01-01-27-019 JPAL-SW-ET04-LS-120228 1.02 95.4 111 

GLPl 0-01-01-27-020 JPAL-SW-ET04-HS-120228 8.96 89.1 109 

Average Concentration (ng/mL) ± VoRPD/RSD 0.0677ng/mL ±9.6% 111% ±1.1% 

NA = Not /Applicable 

Table 14. Trip Blank 120228 

PFOA "C4PFOA 

3M LIMS ID Description 

Concentration 

(ng/mL) VoRecovery %Recovery 

GLPl 0-01-01-27-025 JPAL-SW-TR1P1 -0-120228 <0.0240 NA 101 

GLPl 0-01-01-27-026 JPAL-SW-TR1P1-LS-120228 0.955 95.7 118 

GLPl 0-01-01-27-027 JPAL-SW-TRIP1-HS-120228 9.16 91.8 112 

NA = Not Applicable 

Page 17 of 61 
9 Conclusion 

Laboratory control spikes and field matrix spikes were used to determine the analytical metiiod 

accuracy and precision for PFOA. /Analysis was successfully completed following 3M Environmental 

Laboratory metiiod ETS-8-044.1 described herein. 

10 Data/Sample Retention 

All remaining samples and associated project data (hardcopy and electronic) will be archived according 

to 3M Environmental Laboratory standard operating procedures. 

11 Attactiments 

Attachment A: Protocol /Amendment 27 (General Project Outiine) 

Attachment B: Representative Chromatograms and Calibration Curves 

Attachment C: Analytical Method - ETS-8-044.1 

Page 18 of 61 
GLP10-01-01; Interim Report 27 

Analysis of PFOA in Surface Water 

Bert Jeffries Landfill - February 2012 

12 Signatures 

Cleston Lange, Ph.D., 3M Principal Analytical Investigator Date 

William K. Reagen, Ph.D., 3M Environmental Laboratory Manager Date 

Gary Hohen^ein, 3M Sponsor Representative Date 

Jaisimha Kesari, Study Director Date 

Page 19 of 61 
GLP10-01-01; Interim Report 27 

Analysis of PFOA In Surface Water 

Bert Jeffries Landfill - February 2012 

ATTACHMENT A: PROTOCOL AMENDMENT 

Page 20 of 61 
GLP10-01-01; Interim Report 27 

Analysis of PFOA in Surface Water 

Bert Jeffries Landfill - February 2012 

Analytical Protocol: GLP10-01-01 

Amendment 27 

Study Title 

Analysis of Perfluorooctanoic Acid (PFOA) in Groundwater, Soil and Sediment for the 

31V1 Decatur Phase 3 Site-Related Monitoring Progrann 

PROTOCOL AMENDMENT NO. 27 

Amendment Date: 

February 21, 2012 

Performing Laboratory \ 

3M Environmental, Health, and Safety Operations 

3M Environmental Laboratory 

Building 260-5N-17 

Maplewood, MN 55144-1000 

Laboratory Project Identification 

GLPlO-01-01-27 i 

Sampling Event \ 

j 

Bert Jeffries Landfill -Surfece Water Sampling 

Page 1 of 6 

Page 21 of 61 
GLPl 0-01-01; interim Report 27 

Analysis of PFOA in Surface Water 

Bert Jeffries Landflll - February 2012 

Analytical Protocol: GLP10-01-01 

I Amendment 27 

This amendment modifies the following portion of protocol: 

! 

"Analysis of Perfluorooctanoic Acid (PFOA) in Groundwater, Soil and Sediment for the 

3M Decatur Phase 3 Site-Related Monitoring Program" 

PBOTOCOi. READS: 

No changes to the wording of the protocol are required. 

AMEND TO READ: i 

i 

i 

No changes to the wording of the protocol are required. This amendnrient only addresses and documents 

the addition of the General Project Outline (GPO) for the collection and analysis of groundwater samples 

at Decatur, AL, and conducted as part of the 3M Decatur Phase 3 Prdgram for PFOA (GLPl 0-01-01). 

Sampling activities at and near the Bert Jeffries landfill are scheduled jfor the week of February 27, 2012 

and will consist of 6 paired surface water and sediment samples. This protocol amendment addresses 

the sampling and analysis of the surface water samples. Surface water samples collected under this 

sampling event will be entered into the 3M Environmental Laboratory LiMS as project GLPlO-01-01-27 

and reported as interim report GLPlO-01-01-27, (reflecting study GLP10-01-01 and amendment -27). 

Reason: | 

f 

The reason for this amendment is to document the General Project Outline (GPO) which describes the 

anticipated surface water sample collection event to be conducted at and near the Bert Jeffries landfill in 

Lawrence County,. AL. ! 

The GPO is three pages in length and included as attached to this amendment forni. 

Page 2 of 6 

Page 22 of 61 
GLP10-01-01; Interim Report 27 

Analysis of PFOA in Surface Water 

Bert Jeffries Landfill - February 2012 

Analytical Protocol: GLP1Q-01-01 

I Amendment 27 

Amendment Approval 

21. /2, 

Gary Hohenstein, Sponsor Representative Date 

Cleston Date C. Lange, Principal/Analytical Investigator 

William Reagen, EHS Opns Environmental Lab Management 

Jaisimha Kesarf P.E., DEE, Study Director 

Date 

7h 

Page 3 of 6 

Page 23 of 61 
GLP10-01-01; Interim Report 27 

Analysis of PFOA in Surface Water 

Bert Jeffries Landfill - February 2012 

Analytical Protocol: GLP10-01-01 

Amendment 27 

Environmental Health & Safety Operations, Environmental Laboratory 

General Project Outiine ; 

To: Gary Hohenstein, 3M EHS&Opns 

From: Susan Wolf, 3M EHS&Opns; Environmental Lab I 

cc: VWIliam Reagen, 3M EHS&Opns; Environmental Lab 

Jai Kesari, Weston Solutions 

Charles Young, Weston Solutions '• 

Date: Febmary 21,2012 , 

Subject: Analysis of Perfluorooctanoic Acid (PFOA) in Groundwater, Soil and Sediment for ttie 3M 

Decatur Phase 3 Site-Related Monitoring Program; GLP Interim Report 27 - Bert Jeffries 

Landfill; Surface Water sampling the week of Febmary 27i 2012. 

1 General Project Information 

Contacts 

3M Sponsor Representative 

Gary Hohenstein j 

3M EHS Operations 

3M Building 224-5W-03 ! 

Saint Paul, MN 55144-1000 

Phone: (651) 737-3570 | 

QahohensteirnSmmm.com | 

3M Environmental Laboratory Management 

William K. Reagen ! 

3M EHS Opns, Environmental Laboratory 

260-5N-17 

651 733-9739 

wkreaoeniamnfim.com 

Principal Analytical Investigator 

Cleston Lange i 

3M EHS Opns, Environmental Laboratory 

260-5N-17 i 

651 733-9860 \ 

eclanae(S)mnnm.com j 

Sampling Coordinator ! 

Timothy Frinak ! 

Weston Solutions | 

Timothv.frinak(SwBstonsolution3.com 

Phone: (334)-332-9123 | 

Lab Request Number GLP10J)1^1.27 

Six Digit Department Number Dept #530711, Pixjject #0022674449 

Project Schedule/Test Dates Tentatively scheduled for the week of February 27, 2012. 

All v$rl)al and written correspondence will bs directed to Gary Hohenstein and Jai Kesari. 

Page 4 of 6 

Page 24 of 61 
GLPl 0-01-01; Interim Report 27 

Analysis of PFOA in Surface Water 

Bert Jeffries Landfill - February 2012 

Analytical Protocol: GLP10-01-01 

I Amendment 27 

2 Background Information and Project Objective(s) 

The 3M EHS Operations Laboratory (3M Environmental Lab) will receive and analyze surface water 

samples collected from six (6) locations at and near the Bert Jeffries landfill. Surface water samples will 

be collected by Weston. The 3M Environmental Laboratory will prepare the sample bottles. Samples will 

be analyzed for Perfluorooctanoic Acid (PFOA). Analyses will be conclucted under the GLP requirements 

of EPA TSCA Good Laboratory Practice Standards 40 CFR 792. 

The final report will be submitted to Gary Hohenstein and Jai Kesari upon completion under interim report 

GLPlO-01-01-27. 

I 

3 Project Schedule j 

i 

Sample collection bottles will be prepared by the 3M Environmental Laboratory. Sample bottles will be shipped 

in coolers overnight to 3M Decatur for anival by Friday, February 24, 2012. Sample bottles should be stored 

refrigerated on-site until sample collection. 

Martin Smith \ Weston Trailer 

3M Decatur Plant I 

1400 State Docks Road | 

Decatur, Alabama 35601 i 

! 

4 Test Parameters I 

The targeted limit of quantitation will be 0.025 ng/mL (ppb) for PFOA. 

A total of six,sampling locations have been specified. For each sampling location, a total of lour sample bottles 

will be collected (sample, sample duplicate, low-level field matrix spike, arid high-level field matrix spike). The "fill 

to here" line on each 250 mL Nalgene bottle will be 200 mL. One set of trjp blanks consisting of reagent-grade 

vrater, a low-level trip blank spike, and a high-level trip blank spike vwll be prepared at ttie 3M Environmental 

Laboratory and sent to the sampling location with the other bottles. No previous data on fluonxhemicals in 

groundwater, surface water or sediment media exist for the site. The taw field matrix spike will be prepared at 1 

ng/mL and the high field matrix spike at 10 ng/mL. 

All sample bottles vwll include the addition of "Cg-PFOA (intemal standard) at a nominal concentration of 1 

ng/mL and "C4-PFOA (surrogate recovery standard) at a nominal conceritration of 0.1 ng/mL. 

To aid in sample collection, a non-spiked 1 -L sample bottle will be provided for each sampling location. 

Sample collection will consist of direct immersion. Aliquots will be decanted from the collection bottle to 

the primary, duplicate and matrix spike botties. No rinseate blank will be collected. 

5 Test Methods 

Samples will be prepared and analyzed by LC/MS/WIS following ETS-8-044.1 "Method of Analysis for the 

Detenriination of Perfiuorinated Compounds In Water by High Performance Liquid Chromatography/Mass 

Spectrometry Direct injection Analysis". Altemately, samples may be analyzed by ETS 8-154,3 "Determination 

of Perfluorinated Acids, Alcohols, /\mides, and Sulfonates In Water By Solid Phase Extraction and High 

Performance Liquid Chromatography/Mass Spectrometry, 

Where applicable, samples will be analyzed against an intemal standard calibration cun/e. Each curve point will 

contain isotopioally-labeled PFOA at a nominal concentration of 1 ng/mL.; The calibrafion curve will be 

Page 5 of 6 

Page 25 of 61 
GLPl 0-01-01; Interim Report 27 

Analysis of PFOA in Surface Water 

Bert Jeffries Landfill - February 2012 

Analytical Protocol: GLP10-01-01 

Amendment 27 

generated by taking the ratio of the standard peak area counts over the intemal standard peak area counts to fit 

the data for each analyte. | 

Laboratory control samples prepared with the samples must have an average recovery within 100±20% and a 

RSD s20%. The data quality objective for this study is quantitative results for the target analytes with an 

analytical accuracy of 100±30%. Field matrix spikes not yielding recoveries within 100±30% will be addressed 

in the report and the final accuracy statement may be adjusted accordingly. 

6 Reporting Requirements 

For each sampling location, the report will contain the results for the sample, sample duplicate, and the two field 

matrix spikes. Trip blank and trip blank spikes will be reported for the sampling event Laboratory contnDl 

spikes of reagent water prepared at the time of sample extraction will alsoibe reported and used to evaluate the 

overall method accuracy and precision. Mettiod blanks of reagent water prepared at the time of sample 

preparation will be used to detennine ttne method detection limit For those sampling locations where the field 

matrix spike level was not appropriate due to higher than expected analyte concentrations, a target analyte 

laboratory matrix spike may be prepared and will be included in the final report. 

Page 6 of 6 

Page 26 of 61 
GLP10-01-01; Interim Report 27 

Analysis of PFOA in Surface Water 

Bert Jeffries Landfill - February 2012 

ATTACHMENT B : REPRESENTATIVE SAMPLE CHROMATOGRAMS AND 

CALIBRATION CURVE(S) 

Page 27 of 61 
GLPl 0-01-01; Interim Report 27 

Analysis of PFOA in Surface Water 

Bert Jeffries Landfill - February 2012 

Ginger AG01330509 Results Name: gl20306a.rdb 

40 45 50 55 

Analyte Cone. / IS Cone. 

Data printe d by KJU 

Printin g Time: 1:17:18 PM 

Printin g Date: Monday, March 12, 2012 

Page 1 of 1 

Page 28 of 61 
GLP10-01-01; Interim Report 27 

Analysis of PFOA in Surface Water 

Bert Jeffries Landfill - February 2012 

Ginger AG01330509 Results Name: gl20306a.rdb 

Data printe d by KJU 

Printin g Time: 1:17:39 PM 

Printin g Date: Monday, March 12, 2012 

Page 1 of 1 

Page 29 of 61 
GLP10-01-01; Interim Report 27 

Analysis of PFOA in Surface Water 

Bert Jeffries Landfill - February 2012 

Ginger AG01330509 Results Name: gl20306a.rdb 

Data printe d by STW 

Printin g Time: 8:14:25 AM 

Printin g Date: Wednesday, Apri l 11 

Page 30 of 61 
GLPl 0-01-01; Interim Report 27 

Analysis of PFOA in Surface Water 

Bert Jeffries Landfill - February 2012 

Ginger AG01330509 Result s Name: gl20306a.rdb 

Data printe d by STW 

Printin g Time: 8:14:25 AM 

Printin g Date: Wednesday, Apri l 11 , 2012 

Page 2 o f 9 

Page 31 of 61 
GLPl 0-01-01; Interim Report 27 

Analysis of PFOA in Surface Water 

Bert Jeffries Landfill - February 2012 

Ginger AG01330509 Result s Name: gl20306a.rdb 

Data printe d by STW 

Printin g Time: 8:14:26 AM 

Printin g Date: Wednesday, Apri l 11, 

Page 3 o f 9 

Page 32 of 61 
GLP10-01-01; Interim Report 27 

Analysis of PFOA in Surface Water 

Bert Jeffries Landfill - February 2012 

Ginger AG01330509 Result s Name: gl20306a.rdb 

I

Sampte Name. •g1203068014- Sample ID, "11012-6-6- Fte' •al20306a.wir 

pMk Name: "laCflPFOA-ISIIS)- Mass(Bs), -421.0/376.0 

Comment. ng/mL FC Std m SynBi. WalBi' AnnolaUon* 

Sanple Index: 14 

Sapple Type: Standacd 

Concentration; 1.00 ng/iaL 

Calculate d Cone: N/A 

Acq. Date: 3/6/2012 

Acq. Timet 7:38:06 PM 

Hin. Paak Height: 

Min. Peak width ; 

melliQua r 

0.00 c 

0.00 : 

i pc 

30.0 ; 

Height: 

Star t Tic 

End lim e 

Valle y 

i : 15.5 

975860 COI 

3.12e*005 

15.3 

I Sampte Name'•9l20306a02r Sample ID. •12001-160- F»6,-91203068.wir 

• P«akNan>e •13C8PFOA-IS<IS)- Mass(es),-421.0/376.0 

I CommenL "Malhod Blank- Aruiotaiion. " 

Sample Index: 27 

Sample Type: Unknown 

Concentration; 1.00 ng/nl. 

Calculated Cone: tl/A 

Acq. Date: 3/7/2012 

Min. Peak Height: 

Kin . Peak Hidth : 

Smoothing Width: 

RT WlndOM. 

ExpecCed RT: 

Use Relative RT; 

Height: 

Start 1 

End Tir 

I

Sampla Name: -g120306a028' Sample ID' TCS-120306-1- Fie: -g120306a.wir 

Peak Name: -13C8PFOA-IS(IS}' Ma££(es). '421.0/376.0 

Comment. "OJppb LCS" Annotation " 

Sample In< 

mplB Type 

Concentiatlon 0.99 

Calculated Cone; N 

Acq. Date: 3/7/. 

Acq. Tine ; 12:3 

Modified : 

Hin . Peak HeightMin. Peak width : 

OC 

.telliQua t 

0.00 I 

0.00 ! 

Valley 

15.5 

795655 cc 

Start 1 

End Tip 

I

Sampte Name: *g120306a031" Sampla ID' •LCS-120306^- Ftte' "01203063. 

PeakName -13C8PFOA-IS(IS)' Mass(BS):"421.0/376.0 

Comment "Zppb LCS' AnnotaSon:" 

Modified : 

ETDC. Algorithm: 1 

Mm. Peak Height: 

Hin . Peak Hldth : 

Smoothing width : 

RT Mindo»: 

Expected RT: 

telliCua n - IQA 

O.OO cps 

0.00 sec 

Height: 

Start TJ 

End Timt 

2.79e'005 

Data printe d by STW 

Printin g Time: 8:14:26 AM 

Printin g Date: Wednesday, Apri l 

Page 4 o f 

Page 33 of 61 
GLPl 0-01-01; Interim Report 27 

Analysis of PFOA in Surface Water 

Bert Jeffries Landfill - February 2012 

Ginger flG01330509 Result s Name: gl20306a.rdb 

Data printe d by STW 

Printin g Time: 8:14:26 AM 

Printin g Date: Wednesday, Apri l 11 

Page 

Page 34 of 61 
GLP10-01-01; Interim Report 27 

Analysis of PFOA In Surt'ace Water 

Bert Jeffries Landfill - February 2012 

Ginger AG01330509 Result s Name: gl20306a.rdb 

!

Samp4eName •g120306a053" Sampte ID. •GLPlO-01-01-27-009' F»e:'91203063.wir 

PeakNanw*l3C8PFOA-IS(IS)' Mass(M). "421.0/376,0 

Comnnant •JPAL-SW-ET02-0' Annotation, ~ 

. Algorithm: 

Peak Height: 

Peak Width. 

2.32e*005 

I

Sample Name: 'g120306a060- Sample ID; "GLPl 0-01-01-27-015" Fie: "fl120306a.witr 

Peak Name: •13C8PFOA-IS(IS)- Mass{as) '421.0/376.0 

Comment: 'JPAL-SW-ETOS-LS* Annotation'" 

Sample Index: 60 

Sanple Type: 

Concentration; 

Calculated Cone 

Ptoc. Algol 

Min. Peak Height 

Min. e^ak H. 

Snoothing H. 

Expected BT 

Height; 

1.00 ng/mL 

N/A 2.405 

3/7/2012 2.3e5 

2.2eS 

IntelliQua n - IQA 2.1eS 

: 0.00 cps 

0.00 sec 

2.0e5 

3 points 1.9e5 

15.5 min I.BeS 

No 1.7B5 

Valley 

15.5 min 

1.6eS 

65495 counts I.SeS 

15.3 min 1.4eS 

1.3eS 

£• 1.2e5 Inteti! 

l.leS 

I.OeS 

9.0e4 

8.0O4 

7.0e4 

6.0e4 

5.0e4 

4.0e4 

3.0e4 

2.0*4 

1.0e4 

0.0 

Data printe d by STW 

Printin g Time: 8:14:27 AM 

Printin g Date: Wednesday, Apri l 11, 2012 

Page 

Page 35 of 61 
GLP10-01-01; Interim Report 27 

Analysis of PFOA in Surface Water 

Bert Jeffries Landfill - February 2012 

Ginger AG01330509 Result s Name: gl20306a.rd b 

II Sample Name"g1203D6a014' Sample ID: '11012-6-6- Flo: -g120306a.wjr 

Peak Name:'PFOA- Massfes) '413.0/369.0 amu,413.0/219.0 amu,413.0/169.0 amu* 

II Commam: "OJS ng/triL FC std In Synlh. Water* AnnotaUor: 

0.240 

0.271 

t/6/2012 

I

-Peak Name'-PFOA- Masses). •413.0ra69.0 ai 

Comnrwnf •0.2ppb LCS- Anrtotabon " 

Sample Index: 26 

Sample Type; OC 

Concentration; 0.190 ng/ 

Calculated Cone: 0.1&2 ng/ 

Acq. Date: 3/7/2012 

Modified . 

RT Hindov; 

Expected RT: 

Use Relativ e RT. 

15.0 15.5 16.0 16.5 17.0 17.5 

3271 3380 3489 3598 3707 3816 

Tlrt>e, rrtn 

I

Sampte Name: •gl20306a02T- Sampte ID'-12001-160' Fla'•a120306a.wir 

Peak Name: 'PFOA' UBSs(et) "413.0/369.0 amu,413.0/219.0 emu,413.0/169.0 ai 

Comment 'Method Blank' Annotation-" 

Sanple Index: 27 

Proc. Algorithm: 

Hin . Peak Height: 

Min. Peak Midth : 

Smooching width : 

Use Relatii. 

Base To Ease 

I Sampte Name--Bl20306aO28" Sampte ID. •LCS-120306-T Rte:'9120306a.wifT I

Sampte Name- -g120306a031' Sampte ID- 'LCS-120306-4' Fite: 'g120306a.wi(r 

PeakName 'PFOA' Uass(e£)-'413.0/369.0amu,413.0/2190amu.413.0/16g.0amu' 

Comment *2ppb LCS' Annotatioo' ~ 

;ample Index: 31 

14JS 

_7v_ 

Calculated Cone: 

Acq. Date. 

Acq. Time7.5e5 

7.0e5 

6.5e5 

e.0e5 

5.5e5 

5.0e5' 

S 3,5e5-

30e5' 

2.5e5-

2.0e5' 

Data printe d by STW 

Printin g Time: 8:14:27 AM 

Printin g Date: Wednesday, Apri l 11 , 2012 

15.0 15.5 16.0 16.5 17.0 17.5 

3271 3380 3489 3598 3707 3816 1 15.88 

A. 

Page 7 o f 9 

Page 36 of 61 
GLPl 0-01-01; Interim Report 27 

Analysis of PFOA in Surface Water 

Bert Jeffries Landfill - February 2012 

*** Ginger AG01330509 Result s Name: gl20306a.rd b 

I Sampte Name 'g1203DGa034- Sampte 10: TCS-12D306-7* Fla''g120306a.wiir 

5.0e6' 

4.ee6' 

3.8e6 

3.6e6 

3.4e6 

3.2e6 

3.0e6 

2.ee6 

2.6fl6 

2.4e6 

2.2e6 

2.0e6 

1.8e6 

1.6e6 

8.0e5 

6.0e5-

4.005 

2X)t,5-

153 ^ 

3469 3598 

I

Sampte Name. -91203068041' Sampte 10 -GLPl 0-01-01-27-025" Fite. 'g120306a.wir 

Peak Name -PFOA' Massfes). '413.0/369.0 amu,413.0/219.0 amu.413.0/169.0 amu' 

Comment "JPAL-SW-TRIPI-C Annoialion " 

Sanple Index: 11 

Sanple Type: Unknown 

nthra; IntelliOua 

Smoothing Wic 

BT Window: 

Expected RT: 

I Sampte Name: •g120306a04r Sampte ID: •GLP1CKI1-O1-27-026" I Sample Name •g12O306aO45' Sampte ID "GLPl 0-01-01-27-005' Fite:'g120306a.wir 

Peak Name:-PFOA- Mass<es) '413.0/369.0 armi,413.0/219.0 amu, 

I Comment:'JPAL-SW-TRIPI-LS' Annotation ~ 

Concentiatlon; 

Calculated Cone: 

Acq. Date; 

Peak Name: 'PFOA' Mass(es)' "413,0/369.0 ai 

• Comment-JPAL-SW-ETOI-O- Annotation:' 

Sample Index: 45 

Sample Type; Unknown 

3.ee5 

3.6a5 

3.4e5 

3.2aS 

3,0e5 

2.8e5 

2.Se5 

2/4e5 

2.2*5 

2.0o5-

1.285-

1.0e5-

Proc Algoi 

Noise Perec 

Base. Sub. WindoH 

Peak-Split. Factoi 

Peport Larg> 

Hin. Peak Height 

Min. Peak Width; 

Peak: 

Data printe d by STW 

Printin g Time: 8:14:27 AM 

Printin g Date: Wednesday, Apri l 11, 

Page 

Page 37 of 61 
GLP10-01-01; Interim Report 27 

Analysis of PFOA in Surface Water 

Bert Jeffries Landfill - February 2012 

Ginger AG01330509 Result s Name: gl20306a.rd b 

• Sampte Name -9l20306a053- Sampte ID'*GLP10-01-Ol-27-009' F<e: '9l20306a.wir 

B Peak Name' 'PFOA' Mass(B5): '413.0/369.0 amu,413.0/219,O amu,413.0/169.0amu' 

I I Commam 'JPAL-SW-eT02-0' /Annotation.'" 

Sample Index: 53 

Sacaple Type: Unknown 

Coneentratton; IJ/A 

Calculated Cone: 0.00256 ng/mL 5 

Acq. Date: 3/7/ZOlZ 

Acq Time: 9-24;09 AM 

!. Sub. 

t-Spll i Factoi 

Hin . Peak Height; 

Min. Peak Midth : 

Smoothing Nidth : 

RT Window: 

i BT: 

7.33e»O03 cps 

15.48 

1) 

I Sampte Name'*g12D30&a058' Sampte ID 'GLP10-01-01-27-013" Fite' '9l20306a.wir 

I

Peak Name 'PFOA' Mass(es): '413.0/369.0 ar 

Comment "JPAL-SW-ETOS-O" Annotation: *• 

Sample Index; 58 

Sample Type: Unknown 

Calculated Cone: O.I H ng/mL 

Acq. Date: 3/7/2012 

r: 15.5 

195219 cc 

i.Bie-t-DQt 

15 2 

j,413.0/219.0 emu,413.0/1 G9.0 ai 

13.0 13.5 14.0 14.5 15.0 15.5 16.0 16.5 

2835 2944 3053 3162 3271 ^ 3380 3489 3598 

I

SampteName 'g120306a060" Sampte ID:'GLP10-01-01-27-O15' Rle:-9l20306a,w1fr 

Peak Name' 'PFDA' Mass{es)- "413,0/369.0 amu,413,0/219.0 amu,413.0/169,0 amu' 

Comment' 'JPAL-SW-ET03-LS- Annotation: ~ 

ample Index: 60 

3.B«5-

3.6e5' 

3.4*5 

3.2e5-

ZXS«5-

2£o5 

2.6e5-

2.4e5-

2.205 

2.0e5-

lJe5-

1.6e5-

Modified : 

RT Window: 

Expected RT; 

Height: 

Start Tin 

End Time: 

I Sample Name-'Bl20306a066' Sampte ID 'GLP 10^)1-01-27-017' Fite'•Bl20306a.wifr 

Sample TypeBase. Sub. Window: 

Peak-Split, Factor: 

Report Largest Peal 

Hin. Peak Height: 

Smoothing 

RT Window: 

Expected I 

I 15.87 

i l Data printe d by STW 

Printin g Time: 8:14:28 AM 

Printin g Date: Wednesday, Apri l 11 , 2012 

Page 9 o f 9 

Page 38 of 61 
GLPl 0-01-01; Interim Report 27 

Analysis of PFOA in Surface Water 

Bert Jeffries Landfill - February 2012 

ATTACHMENT C: ANALYTICAL METHOD(S) 

Page 39 of 61 
GLP10-01-01; Interim Report 27 

Analysis of PFOA in Surface Water 

Bert Jeffries Landfill - February 2012 

3M Environmeiital Laboratory 

f\/fethod 

Method of Analysis for the Determination of Perfluorinated Compounds in Water 

by LC/MS/MS; Direct Injection Analysis 

Method Number: ETS-8-044.1 

Adoption Date: 4/12/07 

Effective Date: / //?// / 

Approved By: 

William K. Reagen, Technical Director, Environmental Laboratory Date 

ETS-8-044.1 Page 1 of 22 

Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; Direct 

Injection Analysis 

Page 40 of 61 
GLP10-01-01; Interim Report 27 

Analysis of PFOA in Surface Water 

Bert Jeffries Landfill - February 2012 

1 Scope and Application 

This method describes the direct injection analysis of perfluorinated compounds (PFCs) from 

water matrices using high-perfomiance liquid chromatography tandem mass spectrometry 

(HPLC/MS/MS). The method is generally applicable but not limited to the measurement of 

perfluoroalkyi sulfonamides and perfluorinated alkyI acids (PFAAs) such as perfluorosulfonic 

acids (PFSAs) and perfluorocarboxylic acids (PFCAs) (Table 1). Water samples containing 

heavy particulate may require preparation by an altemate method such as ETS-8-154 

"Detennination of Perfluorinated Acids, Alcohols, Amides, and Sulfonates In Water By Solid 

Phase Extraction and High Performance Liquid Chromatography/Mass Spectrometry". The 

method is applicable to both extemal standard and intemal standard calibration \ 

Table 1. Representative Target Analytes 

Acronym Analyte 

Chemical Abstract Services 

Registry Number (CASRN) 

PFBA (C4 Acid) Perfluorobutanoic acid 375-22-4 

PFPeA (05 Acid) Perfluoropentanoic acid 2706-90-3 

PFHxA (06 Acid) Perfluorohexanoic acid 307-24-4 

PFHpA (07 Acid) Perfluoroheptanoic acid 375-85-9 

PFOA (08 Acid) Perfluorooctanoic acid 335-67-1 

PFNA (09 Acid) Perfluorononanoic acid 375-95-1 

PFDA (010 Acid) Perfluorodecanoic acid 335-76-2 

PFUnA (Oil Acid) Perfluoroundecanoic acid 2058-94-8 

PFDoA (012 Acid) Perfluorododecanoic acid 307-55-1 

PFTrDA (013 Acid) Perfluorotridecanoic acid 72629-94-8 

PFBS (04 Sulfonate) Perfluorobutanesulfonic acid 375-73-5 

PFHS (06 Sulfonate) Perfluorohexanesulfonic acid 355-46-4 

PFOS (08 Sulfonate) Perfluorooctanesulfonic acid 1763-23-1 

FBSA (04 Sulfonamide Perfluorobutanesulfonamide 30334-69-1 

FOSA (08 Sulfonamide) Pefluorooctanesulfonamide 754-91-6 

The Minimum Reporting Level (MRL) is the Limit of Quantitation (LOQ) that meets Data 

Quality Objectives (DQOs) that are developed based on the intended use of this method. 

Method Flexibility - This is a perfomiance-based method and may be generally applied to the 

determination of perfluorinated compounds in water matrices when analysis batch quality 

control (QC) criteria are met^. Each set of samples are prepared in an analysis batch with 

calibration standards, LCSs, blanks, and continuing calibration check standards analyzed on 

the same instrument during a time period that begins and ends with the analysis of the 

appropriate continuing calibration check standards. The laboratory is pennitted to modify the 

LC column, mobile phase composition, LC conditions, and MS/MS conditions. Method 

modifications should be considered to improve method perfomnance or to meet data quality 

objectives for the study. In all cases where method modifications are implemented, the batch 

' The method is supported by validation with intemal standard calibration for C4-C13 PFCAs, C4, C6, and C8 PFSAs, 

and C8 perfluoroalkane sulfonamide in laboratory control samples under 3M method validation El 1-0667. 

^ Guidance for establishing method QC Criteria based on a.) FDA May 2001, "Guidance for Industry, Bioanalytical 

Method Validation", b.) EPA Method 537, and c.) European Commission: Guidance for Generating and Reporting 

Methods of Analysis in Support of Pre-registration Data Requirements for Annex II (Part A, section 4) and Annex III 

(Part A,section 5) of Directive 91/414, SANCO/3029/99 rev. 4 (11/07/00). 

ETS-8-044.1 Page 2 of 22 

Method of Analysis for the Determination of Perfluorinated Compounds in Water by LC/MS/MS; 

Direct Injection Analysis 

Page 41 of 61 
GLP10-01-01; Interim Report 27 

Analysis of PFOA in Surface Water 

Bert Jeffries Landfill - February 2012 

analytical QCs (section 9) must be completed and pass QC acceptance criteria (section 13) if 

the data from the analytical batch are to be reported. 

2 Method Summary 

Water samples are analyzed as neat aqueous sample or as solvent diluted aqueous samples 

by direct injection using LC/MS/MS. Samples containing heavy particulate may not be 

suitable for analysis by this method. Samples containing suspended particulate should be 

centrifuged or filtered prior to removing a sample aliquot or diluting with solvent. The water 

sample is mixed well prior to removing an aliquot or diluting, if necessary, with ASTM Type I 

water, HPLC water, other suitable water, or solvent (methanol). 

Quantitation is by stable isotope internal standard calibration in laboratory reagent water. All 

perfluorinated compounds (PFCs) target analyte concentrations of perfluorosulfonic acids 

(PFSAs) and perfluorocarboxylic acids (PFCAs) are reported as anions and corrected for 

their salt or free acid fomns. Altematively, quantitation may be perfonned by extemal 

standard calibration. 

This is a perfomnance-based method. Method uncertainty for each target analyte is 

detennined for each analytical batch using multiple laboratory control spikes at multiple 

concentrations. This method also requires that the precision and accuracy for each sample 

be detennined using field matrix spikes to verify that the method is applicable to each sample 

matrix. 

Calibration standards for PFUnA, PFDoA, PFTrDA, and FOSA have been found to be 

unstable for more than 2 days in 100% water. Samples requiring analysis for these 

compounds by this method should be diluted 1:1 with methanol and analyzed against a 

calibration curve prepared in 1:1 synthetic groundwaterMeOH. 

3 Definitions 

3.1 Analysis Batch 

A set of study samples that are prepared with calibration standards, laboratory control 

samples, and procedural blanks, and analyzed on the same instmment during a time period 

that begins and ends with the analysis of the appropriate continuing calibration check 

standards. 

3.2 Analytical Sample 

A portion of a laboratory sample prepared for analysis. 

3.3 Calibration Standard 

A solution prepared by spiking a known volume of the Working Standard (WS) into a 

predetennined amount of ASTM Type I, HPLC grade water, or other suitable water (i.e. 

matrix water), and analyzed according to this method. Calibration standards are used to 

calibrate the instrument response with respect to analyte concentration. 

3.4 Laboratory Duplicate Sample (LDS, or Lab Dup) 

A laboratory duplicate sample is a separate aliquot of a sample taken in the analytical 

laboratory that is analyzed separately with identical procedures. Analysis of LDSs compared 

to that of the first aliquot give a measure of the precision associated with laboratory 

procedures, but not with sample collection, preservation, or storage procedures. 

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Bert Jeffries Landfill - February 2012 

3.5 Field Blank (FB)/Trip Blank (TB) 

ASTM Type I, HPLC grade water, or other suitable water, placed in a sample container in the 

laboratory and treated as a sample in ail respects, including exposure to sampling site 

conditions, storage, preservation and all analytical procedures. The purpose of the TB is to 

determine if test substances or other interferences are present in the field environment. This 

sample is also referred to as a Trip Blank. 

3.6 Field Duplicate Sample (FDS, Field Dup) 

A sample collected in duplicate at the same time from the same location as the sample. The 

FDS is handled under identical circumstances and treated exactly the same throughout field 

and laboratory procedures. Analysis of the FDS compared to that of the first sample gives a 

measure of the precision associated with sample collection, preservation and storage, as well 

as with laboratory procedures. 

3.7 Field Matrix Spike (FMS) 

A sample to which known quantities of the target analytes, ISs and SRSs are added to the 

sample bottle in the laboratory before the bottles are sent to the field for collection of aqueous 

samples. A known, specific volume of sample must be added to the sample container 

without rinsing. This may be accomplished by making a "fill to this level" line on the outside of 

the sample container. The FMS is analyzed to ascertain if any matrix effects, interferences, 

or stability issues may complicate the interpretation of the sample analysis. 

3.8 Trip Blank Matrix Spike (TBMS) 

An aliquot of ASTM Type I, HPLC grade water, or other suitable water, to which known 

quantities of the target analytes, ISs and SRSs are added in the laboratory prior to the 

shipment of the collection bottles. The TBMS is analyzed exactly like a study sample to help 

detemnine if the method is in control and whether a loss of analyte or analytical bias could be 

attributed to sample holding time, sample storage and/or shipment issues. A low and high 

TBMS are appropriate when expected sample concentrations are not known or may vary. 

3.9 Internal Standard (IS) 

A compound added to each study sample, calibration standard, laboratory control samples, 

and procedural blanks at a consistent level (typically around 1 ng/mL). The intemal 

standard(s) are stable isotope labeled versions of the target analytes. The area count ratio of 

the target analyte to the intemal standard is used for calibration. Surrogate ISs are applied 

when stable isotope ISs of target analytes are unavailable. A sun-ogate IS is not necessarily 

a stable isotope labeled version of the target analyte, but is treated as an internal standard for 

quantitation. 

3.10 Laboratory Control Sample (LCS) 

An aliquot of control matrix to which known quantities of the target analytes, ISs and SRSs 

(when applicable) are added in the laboratory at the time when samples are aliquotted. At 

least three levels (two levels for SRSs) in triplicate are included, one generally at the low end 

of the calibration curve and one near the mid range and the upper end of the curve. The 

LCSs are analyzed exactly like a laboratory sample to detennine whether the stability of the 

standards. LCSs should be prepared each day samples are aliquoted. 

3.11 Laboratory Matrix Spike (LMS) 

A laboratory matrix spike is an aliquot of a sample to which known quantities of target 

analytes, ISs and SRSs (when applicable) are added in the laboratory. The LMS is analyzed 

exactly like a laboratory sample to determine whether the sample matrix contributes bias to 

the analytical results. The endogenous concentrations of the analytes in the sample matrix 

must be determined in a separate aliquot and the measured values in the LMS corrected for 

these concentrations. LMSs are optional for analysis of aqueous samples. 

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Bert Jeffries Landfill - February 2012 

3.12 Laboratory Sample 

A portion or aliquot of a sample received from the field for testing. 

3.13 Limit of Quantitation (LOQ) 

The lower limit of quantitation (LLOQ) for an analytical batch is the lowest concentration that 

can be reliably quantitated within the specified limits of precision and accuracy. The LLOQ is 

generally selected as the lowest non-zero standard in the calibration curve that meets method 

acceptance criteria. The LLOQ for each target analyte is established for each analysis batch 

as the lowest calibration standard with area counts at least twice that of the average area 

counts of the procedural blanks. 

The upper limit of quantitation (ULOQ) for an analytical batch is the highest concentration that 

can be reliably quantitated within the specified limits of precision and accuracy. The highest 

standard in the calibration curve that meets method acceptance criteria is defined as the 

ULOQ. 

3.14 Method/Procedural Blank 

An aliquot of control matrix that is treated exactly like a laboratory sample including exposure 

to all glassware, equipment, solvents, and reagents that are used with other laboratory 

samples. The method blank is used to detennine if test substances or other interferences are 

present in the laboratory environment, the reagents, or the apparatus. 

3.15 Sample 

A sample is an aliquot removed from a larger quantity of material intended to represent the 

original source material. 

3.16 Stock Standard Solution (SSS) 

A concentrated solution of a single-analyte prepared in the laboratory with an assayed 

reference compound. 

3.17 Surrogate Internal Standard 

An IS that is not necessarily a stable isotopically labeled target analyte, but is treated as an 

intemal standard for quantitation. Sun-ogate ISs are used when isotopically labeled 

counterparts of the target analyte are not commercially or readily available. 

3.18 Surrogate Recovery Standard (SRS) 

An isotopically labeled standard, not used as an internal standard, that is added to each 

sample and appropriate QC sample as a means to evaluate the method performance for a 

chemical class of compounds (e.g., PFSAs, PFCAs). 

3.19 Working Standard (WS) 

A solution of several analytes prepared in the laboratory from SSSs and diluted as needed to 

prepare calibration standards and other required analyte solutions. 

4 Warnings and Cautions 

4.1 Health and Safety 

The acute and chronic toxicity of the standards for this method have not been precisely 

detennined; however, each should be treated as a potential health hazard. The analyst 

should wear gloves, a lab coat, and safety glasses to prevent exposure to chemicals that 

might be present. 

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Bert Jeffries Landfill - February 2012 

The laboratory is responsible for maintaining a safe work environment and a current 

awareness of local regulations regarding the handling of the chemicals used in this method. 

A reference file of material safety data sheets (MSDS) should be available to all personnel 

involved in these analyses. 

4.2 Cautions 

The analyst must be familiar with the laboratory equipment and potential hazards including, 

but not limited to, the use of solvents, pressurized gas and solvent lines, high voltage, and 

vacuum systems. Refer to the appropriate equipment procedure or operator manual for 

additional infomnation and cautions. 

5 Interferences 

During sample preparation and analysis, major potential contaminant sources are reagents 

and glassware. All materials used in the analyses shall be demonstrated to be free from 

interi'erences under conditions of analysis by running method blanks. 

Parts and supplies that contain Teflon® should be avoided or minimized due to the possibility 

of interference and/or contamination. These may include, but are not limited to: wash bottles. 

Teflon® lined caps, autovial caps, HPLC parts, etc. 

The use of disposable micropipettes or pipettes to aliquot standard solutions is recommended 

to make calibration standards and matrix spikes. 

6 Instrumentation, Supplies, and Materials 

6.1 Instrumentation 

Analytical balance capable of reading to 0.0001 g 

HPLC/MS/MS or HPLC/MS system, as described in Section 10. 

6.2 Supplies and Materials 

Sample collection bottles—HDPE (e.g., NalgeneTM) wide-mouth bottles with screw cap. 

Note: Do not use fluorinated or Teflon® bottles or lined caps. 

Coolers or boxes for sample shipment. 

15-mL and 50-mL disposable polypropylene centrifuge tubes. 

Class A pipettes and volumetric flasks, various. 

2 mL HPLC autovials 

Disposable pipettes, polypropylene or glass as appropriate 

Centrifuge capable of spinning 15-mL and 50-mL polypropylene tubes at 3000 rpm. 

7 Reagents and Standards 

Note: Suppliers and catalog numbers are for illustrative purposes only. Equivalent 

perfomnance may be achieved using chemicals obtained from other suppliers. Do not use a 

lesser grade of chemical than those listed. 

7.1 Chemicals 

Water - Milli-Q, HPLC grade, or other suitably appropriate sources 

Calcium Acetate - A.C.S. Reagent Grade 

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Analysis of PFOA in Surface Water 

Bert Jeffries Landfill - February 2012 

Magnesium Acetate - A.C.S. Reagent Grade 

Methanol - HPLC grade 

Ammonium Acetate -A.C.S. Reagent Grade 

7.2 Representative Target Analytes, ISs, and SRSs 

PFBA, Heptafluorobutyric Acid, (C4 Perfluorinated Acid) 

PFPeA, Nonafluoropentanoic Acid (C5 Perfluorinated Acid) 

PFHxA, Perfluorohexanoic Acid (Ce Perfluorinated Acid) 

PFHpA, Tridecafluoroheptanoic Acid, (C7 Perfluorinated Acid) 

PFOA, Ammonium perfluorooctanoate, (Cs Perfluorinated Acid) 

PFNA, Heptadecafluorononanoic Acid, (C9 Perfluorinated Acid) 

PFDA, Nonadecafluorodecanoic Acid (C10 Perfluorinated Acid) 

PFUnA, Perfluoroundecanoic Acid, (Cn Perfluorinated Acid) 

PFDoA, Perfluorododecanoic Acid, (C12 Perfluorinated Acid) 

PFTriDA, Perfluorotridecanoic Acid, (C13 Perfluorinated Acid) 

FBSA, Perfluorobutanesulfonamide 

FOSA, Perfluorooctanesulfonylamide 

PFBS, Potassium Perfluorobutanesulfonate 

PFHS, Perfluorohexanesulfonate 

PFOS, Potassium perfluorooctanesulfonate 

PFOA [1,2, 3,4-"C], "C4-isotopically labeled perfluorooctanoic acid (SRS) 

PFOS [1,2, 3,4-"C], ^^C4-isotopically labeled Perfluorooctanesulfonate (SRS) 

PFUnA [1,2-"C], "C2-isotopically labeled Perfluoroundecanoic acid (SRS) 

A custom mix of ISs in a methanolic solution containing ([1,2,3,4-"C4]PFBA, {1,2 -

"CJPFHxA, [1,2,3,4,5,6,7,8-"C8]PFOA, [1,2,3,4,5,6,7 8,9-"C9]PFNA, [1,2 -''XdPFDA, 

[1,2,3,4,5,6,7 -"CyjPFUnA, [1,2 -^^CJPFDoA, [1,2,3-^^CsjPFHS, [1,2,3,4,5,6,7,8-^^C8]PFOS, 

and [1,2,3,4,5,6,7,8-"C8]PFOSA (Wellinqton Laboratories, Guelph, ON) in combination with 

added ([1,2,3,4,5-"C5]PFPeA, ([1,2,3,4-X4]PFHpA, and [^^OJPFBS can be used to prepare 

a stock IS solution. Alternatively, individual stable isotope ISs can be used to prepare a stock 

IS mixture. 

Other ISs can be applied. 

7.3 Reagent Preparation 

2 mM Ammonium acetate solution (Analysis)—Weigh 0.3 g of Ammonium acetate and 

dissolve in 2.0 L of reagent water. 

Synthetic Groundwater (containing 25 ppm Ca and Mg) - Weigh 0.61 g of Calcium Acetate 

and 0.92 g of Magnesium Acetate and dissolve in 6.0 L of reagent water. 

Note: Alternative volumes may be prepared as long as the ratios of the solvent to solute ratios 

are maintained. 

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Bert Jeffries Landfill - February 2012 

7.4 Stock Standard Solution (SSS) and Working Standard Solution 

Preparation 

The following standard preparation procedure serves as an example. Weighed amounts and 

flnal volumes may be changed to suit the needs of a particular study. For example, pL 

volumes may be spiked into volumetric flasks when diluting stock solutions to appropriate 

levels. 

100 \iglmL target analyte SSSs—Weigh out 10 mg of analytical standard (corrected for 

percent salt, acid [ETS-4-031] and purity) and dilute to 100 mL with methanol or other 

suitable solvent, in a 100 mL volumetric flask. Transfer to a 125 mL LDPE bottle or other 

suitable container. Prepare a separate solution for each analyte. Expiration dates and 

storage conditions of stock solutions should be assigned in accordance with laboratory 

standard operating procedure. An example of purity and salt con-ection is given below for 

PFOS. 

, , molecular weight of anion 

salt correction factor = = 

moclecular weight of salt 

499 PFOS (K^^ )salt correction factor = — = 0.9275 

. 538 

10 mg CsFiySOsK* with purity 90% = 8.35 mg CsFuSOa"(10 mg*0.90*0.9275=8.35 mg) 

10 \iglmL (10,000 ng/mL) mixed working standard—Add 5.0 mL each of the 100 pg/mL 

SSSs to a 50 mL volumetric flask and bring up to volume with solvent. 

1 (jg/mL (1,000 ng/mL) mixed working standard—Add 0.5 mL of the 100 pg/mL SSSs to a 

50 mL volumetric flask and bring up to volume with solvent. 

0.1 |jg/mL (100 ng/mL) mixed standard—Add 0.05 mL of the 100 pg/mL SSSs to a 50 mL 

volumetric flask and bring up to volume with solvent. 

Storage Conditions—Store all SSSs and worthing standards in accordance with laboratory 

standard operating procedure or in a refrigerator at 4°±2°C for a maximum period of 6 months 

from the date of preparation. 

7.5 Calibration Standards 

Calibration can be perfonned by IS or extemal calibration. Using the worthing standards 

described above, prepare calibration solutions in ASTM Type I water, HPLC water, other 

suitable water, or a mixture of solvent and water using the infomnation in Table 2 as a 

guideline. Note: Volumes of water or water/solvent mixtures and wori<ing standards may be 

adjusted to meet the data quality objectives addressed in the general project outline. 

Calibration levels other than those listed below can be prepared as needed. 

For the quantitation of PFOA and PFOS, reference materials of certifled mixed linear and 

branched isomer are prefen-ed. Altemately, reference materials of primarily linear isomers of 

PFOA and/or PFOS may be used, however, when quantitating with predominantly linear 

reference standards, additional LCS samples containing both linear and branched isomers of 

PFOA and PFOS are required^. 

7.5.1 Internal Standard (IS) and SurTt>gate Recovery Standard (SRS) 

For IS calibration, stable isotope internal standards of each target analyte or appropriate 

surrogate ISs should be spiked at the same level in all calibration standards. Once the 

calibration standards have been prepared as stated above in Section 7.5, all calibration 

standards are spiked with a separate intemal standard spiking solution. Typically the 

' A report summarizing an assessment of the use of reference standards containing certified linear and branched isomers of 

PFOA/PFOS can be found in 3M report Ell-0560. 

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Bert Jeffries Landfill - February 2012 

concentration of the intemal standard is consistent with the intemal standard concentration 

expected in the samples being prepared, usually 1 ng/mL. The concentration of the internal 

standard spiking solution is typically 2 pg/mL. A separate zero point or method blank is 

typically prepared at the same time as the calibration standards, using the same solution 

used to prepare the standards (ASTM Type I water, HPLC water, other suitable water, or a 

solvent/water mixture), and is spiked with the internal standard at the same concentration as 

the calibration curve, typically at 1 ng/mL. 

If the samples being analzyed were pre-spiked with SRSs, the calibration curve prepared in 

Section 7.5 is spiked with a separate SRS spiking solution. Typically, the sample bottles are 

spiked with a SRS at 0.1 ng/mL. The flnal calibration curve must consist of at least six 

calibration points after analysis. The following table provides an example of spike 

concentrations and volumes used to achieve a multi-point extracted calibration curve with 

internal standard and sun-ogate standard. 

Table 1 lists recommended stable isotope internal standards for several PFSA and PFCA 

target compounds. A custom mix of isotopically labeled target analytes in a methanolic 

solution containing ([1,2,3,4-"C4]PFBA, [1,2 -^^CJPFHxA, [1,2,3,4,5,6 7,8-"C8]PFOA, 

ri,2,3,4,5,6,7,8,9-^^C9]PFNA, [1,2,3,4,5,6 -^^CeJPFDA, [1,2,3,4,5,6,7 -^XyjPFUnA, [1,2 -

^^C2]PFDoA, [1,2,3-"C3]PFHS, [1,2,3,4,5,6,7,8-"C8]PFOS, and [1,2,3,4,5,6,7,8-^^C8]FOSA 

(Wellington Laboratories, Guelph, ON) in combination with added ([1,2,3,4,5-''^C5]PFPeA, 

([1,2,3,4-^^C4]PFHpA, and [^^OJPFBS can be used to prepare a stock IS solution. 

Alternative sources of certifled stable isotope labeled target analytes are applicable. 

Alternatively, individual stable isotope ISs can be used to prepare a stock IS mixture. The 

table below lists the recommended stable isotope ISs and SRSs applied in the method. 

Other stable isotope ISs and SRSs of target analytes not listed in the table may be used if 

supported by validation and/or analysis batch QCs meeting method acceptance criteria (e.g., 

["CJ-PFOA). The same internal standard should be used for a given analyte throughout the 

entire project/study. Note: some of the compounds listed below are appropriate to use as 

surrogate ISs when a stable isotope IS of a target analyte is not available. Generally, 

surrogate isotopically labeled PFCAs are used for PFCAs, and sun-ogate isotopically labeled 

PFSAs are used for PFSAs. 

Table 2 provides examples of spike concentrations and volumes used to achieve a multi-point 

calibration curve with ISs and SRSs. 

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Bert Jeffries Landfill - February 2012 

Table 1. Stable Isotope PFCAs and PFSAs used for ISs and SRSs 

Compound Name Synonym or Acronym Analytical Purpose Reference Standard 

Source 

"C4-Perfluorobutanoic acid [1,2,3,4-"C4]PFBA IS for PFBA 

Wellington Labs 

(Mix or Individual) 

"C4-Perfluoropentanoic acid [l,2,3,4,5-"C5]PFPeA IS for PFPeA 

Wellington Labs 

(Mix or Individual) 

"C2-Perfluorohexanoic acid [l,2-"C2]PFHxA IS for PFHxA 

Wellington Labs 

(Mix or Individual) 

"C4-Perfluoroheptanoic acid [l,2,3,4-"C4]PFHpA IS for PFHpA 

Wellington Labs 

(Mix or Individual) 

"Cg-Perfluorooctanoic acid [l,2,3,4,5,6,7,8-"C8]PFOA IS for PFOA and [1,2,3,4 

"C4]PF0A 

Wellington Labs 

(Mix or Individual) 

"Cg-Perfluorononanoic acid [!,2,3,4,5,6,7,8,9-"C,]PFNA IS for PFNA 

Wellington Labs 

(Mix or Individual) 

"Ce-Perfluorodecanoic acid [1,2,3,4,5,6-"C6]PFDA IS for PFDA 

Wellington Labs 

(Mix or Individual) 

"C7-Perfluoroundecanoic acid [1,2,3,4,5,6,7 -"ClPFUnA IS for PFUnA 

Wellington Labs 

(Mix or Individual) 

"C2-Perfluorododecanoic acid [l,2-"C2]PFDoA IS for PFDoA, *PFTA 

Wellington Labs 

(Mix or Individual) 

"Oi-Ammonium Perfluorobutane sulfonate ["02]PFBS IS for PFBS RTI Intemational 

(Individual) 

"C3-Ammonium Perfluorohexane sulfonate [1,2,3-"C3]PFHS IS for PFHS 

Wellington Labs 

(Mix or Individual) 

"Cg-Sodium Perfluorooctane sulfonate [l,2,3,4,5,6,7,8-"C8]PFOS IS for PFOS and 

PFOS[l,2,3,4 "C4], 

Wellington Labs 

(Mix or Individual) 

"Cg-Perfluorooctanesulfonamide [l,2,3,4,5,6,7,8-"C8]FOSA IS for FOSA 

Wellington Labs (mix) 

RTI Intemational 

(Individual) 

"C4-Perfluorooctanoic acid [l,2,3,4-"C4]PFOA SRS for all PFCAs: C4-C8 Wellington 

"C2-Perfluoroundecanoic acid [1,2 -"C2]PFUnA SRS for all PFCAs C9-C13 Wellington 

"Cg-Perfluorooctane sulfonate [l,2,3,4-"C4]PFOS SRS for all PFSAs: C4, 

C6, and C8 Wellington 

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Bert Jeffries Landfill - February 2012 

Table 2. Example Preparation of Calibration Curve with ISs and SRSs 

Sample Description Concentration 

ofWS.tig/mL 

Volume of 

WS.fd. 

Volume of IS 

(2 fjg/mL), fd. 

Concentration of 

Surrogate, fig/mL 

Volume of 

Surrogate, /jL 

Volume of ASTM Type 1 Water, or 

other suitable solvent mL 

0.025 ng/mL curve point 0.10 25 50 0.20 12.5 100 

0.030 ng/mL curve point 0.10 30 50 0.20 15 100 

0.04 ng/mL curve point 0.10 40 50 0.20 20 100 

0.05 ng/mL curve point 0.10 50 50 0.20 25 100 

0.1 ng/mL curve point 0.10 100 50 0.20 50 100 

0.25 ng/mL curve point 0.10 250 50 0.20 125 • 100 

0.5 ng/mL curve point 1.0 50 50 0.20 250 100 

1 ng/mL curve point 1.0 100 50 0.20 500 100 

2.5 ng/mL curve point 10.0 25 50 10.0 25 100 

5.0 ng/mL curve point 10.0 50 50 10.0 50 100 

10.0 ng/mL curve point 10.0 100 50 10.0 100 100 

25.0 ng/mL curve point 10.0 250 50 10.0 NA 100 

50.0 ng/mL curve point 10.0 500 50 10.0 NA 100 

75.0 ng/mL curve point 10.0 750 50 10.0 NA 100 

100 ng/mL curve point 10.0 1000 50 10.0 NA 100 

N/A - Not Applicable 

(1) Samples requiring analysis for PFUnA, PFDoA, PFTrDA, and FOSA sfiould be analyzed against a calibration curve prepared in 1:1 synthetic groundwater:MeOH. 

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Bert Jeffries Landfill - February 2012 

8 Sample Collection and Bottle Preparation 

Sample collection bottles are prepared by 3M Environmental Laboratory (or subcontract supplier) personnel for 

shipment at ambient temperature to the collection site. Typically, four separate collection bottles are 

associated with a single collection site: sample, field duplicate sample, low field matrix spike, and high field 

matrix spike. Alternatively, the sample and field duplicate sample may contain SRSs in lieu of additional target 

analyte low field matrix spike and target analyte high field matrix spike samples. Depending on the scope of 

the project, additional replicates of the field sample and field matrix spikes may be added. Also, it is not 

uncommon for additional mid-level field matrix spikes to be collected if the expected sample concentrations are 

truly unknown or could span a large concentration range. 

High-density polyethylene (HDPE) wide-mouth Nalgene bottles are used for the sample collection containers. 

(Volumes of the bottles may vary depending on how much sample is required to meet data quality objectives.) 

Sample collection volumes are project specific and based on data quality objectives. The Nalgene bottles do 

not require any pretreatment prior to use. Typically, placement of a sample bottle volumetric "fill to here" line is 

done by using a sample bottle marker template. Alternatively, bottles may be weighed prior to bottle 

preparation and weighed again after samples have been collected. 

All bottles should be cleariy labeled to indicate its intended use as a sample, field sample duplicate, low field 

matrix spike, high field matrix spike, sample/SRS field matrix spike, field duplicate sample/SRS field matrix 

spike, trip blank, or trip blank matrix spike. If each location has different designated spike levels, the label 

should also cleariy indicate the sample location designation. Generally, a set of bottles for a given collection 

site are prepared then grouped together in plastic bags for organizational purposes. For each sample 

collection event, at least one set of trip blank and trip blank matrix spikes are prepared. 

Bottle preparation should be documented in a Note to File or on a sample preparation wori^sheet and should 

include the following infomiation: date prepared, total number of bottles prepared, number of sample sites, the 

standard'identification numbers and spike volumes used to prepare spiked bottles, the "fill to here" volume, and 

any other pertinent infomnation needed for reconstructibility of the data. The Note to File will be included in the 

final data package for the project. 

Samples are collected in the field and shipped to the laboratory at ambient temperature. 

8.1 Field Matrix Spike Sample (FMS) 

Field matrix spike samples are a requirement of the method. A FMS sample is defined as a QC sample to 

which known quantities of appropriate target analytes are added to the sample bottle in the field or in the 

laboratory before the bottles are sent to the field. The sample and field duplicate sample may contain 

appropriate SRSs in lieu of target analyte FMS samples. Sample quantities are detennined volumetrically or 

gravimetrically. A known, specific volume or weight of sample is added to the sample container without 

rinsing. Volumetric sample measurements may be acquired by a laboratory applied "fill to this level" line on the 

outside of the sample container. Target analyte FMS samples should be spiked at approximately 0.5-10 times 

the expected analyte concentration in the sample. If the expected range of analyte concentrations is unknown, 

multiple spikes at varying levels may be prepared to increase the likelihood that a spike at an appropriate level 

is made. Typically a low and a high target analyte spike are prepared for each sampling location. In those 

instances where SRSs are to be used in lieu of target analyte FMS samples, the sample and field duplicate 

sample are spiked at approximately 2-5 times the target LOQ. The FMS is analyzed to ascertain if matrix 

effects or sample holding time contributes bias to the analytical results. For the sample bottles designated for 

matrix spikes, an appropriate volume of matrix spiking solution is added to the empty bottle prior to sampling. 

The volume of spike solution added should produce the desired final concentration of target analytes once the 

bottle is filled with sample to the "fill to here line". The matrix spiking solution(s) should be prepared in a 

suitable solvent and contain all of the appropriate target analytes, ISs, and SRSs. The target analyte matrix 

spiking solution is often the same as the working standards used to create the calibration standards. An 

example of a bottle spike is given below. 

"Fill to here" volume = 200 mL (A 250 mL Nalgene bottle is used) 

Desired Field Spike Concentration = 0.25 ng/mL 

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500 nL of a 0.1 ixg/mL spiking solution (containing the target analytes) is added to the bottle and the bottle cap 

promptly sealed. 

8.2 Internal Standard and Surrogate Recovery Standard 

If analysis of a sun-ogate recovery standard (SRS) is included in the project objectives, an appropriate volume 

of a sun-ogate standard solution is added to all the bottles prior to sampling and SPE. Typically sample bottles 

are spiked with sun-ogate recovery standards at a final desired spike concentration of 0.1 ng/mL. 

If quantitation by intemal standard (IS) is included in the project objective, an appropriate volume of internal 

standard solution is added to all the bottles prior to sampling and SPE. Typically sample bottles are spiked 

with intemal standard at a final desired spike concentration of 1 ng/mL. 

For the trip blank, the SRS spike and IS spike is added to the bottle and then ASTM Type I water (HPLC grade 

reagent water or other suitable water may used) is added to the "fill to here" line. The bottle is capped and 

sealing tape may be placed around the outer edge of the cap. Trip blank matrix spikes are prepared by adding 

the appropriate volume of target analyte spiking solution, IS, and SRS spiking solutions and filling the bottle to 

the desired volume with the appropriate water and capping and sealing the cap. 

9 Quality Control and Data Quality Objectives 

9.1 Data Quality Objectives 

This method and required quality control samples is designed to generate data accurate to ±30% with a 

targeted LOQ of 0.025 ng/mL. Any deviations from the quality control measures spelled out below will be 

documented in the raw data and footnoted in the final report. 

9.2 Method/Procedural Blanks 

The method/procedural blank is zero point calibration standard (which includes ISs) analyzed in a regular basis 

with each analysis batch. At a minimum, method blanks are analyzed prior to instrument calibration, prior to 

the analysis of CCV samples, after every 10 sample injecfions, and at the end of the analytical njn. 

The mean area count or area ratios when using intemal standard calibration, for each analyte in the method 

blanks must be less than 50% of the area count counts or area ratios when using internal standard calibration, 

of the LOQ standard. The standard deviation of the area counts, or area ratios when using internal standard 

calibration, of these method blanks should be calculated. A specific %RSD acceptance criteria is not specified 

but is assessed on an analytical batch basis. If the mean area counts or area ratios when using internal 

standard calibrafion, of the method blanks exceed 50% of the LOQ standard, then the LOQ must be raised to 

the first standard level in the curve that meets criteria. Method blanks may be eliminated if technical 

justification can be provided (e.g. the procedural blank was analyzed after an unexpectedly high level sample). 

If any procedural blanks are removed from the LOQ determination, document in the raw data and report as 

appropriate. Laboratory Sample Replicates / Field Duplicate Sample 

Typically, samples are collected in duplicates in the field. The relative percent difference (RPD) of duplicate 

samples should be ^20% for the precision of sample preparation and analysis to be considered in control. 

Replicate samples not meeting the 220% RPD criteria are flagged and reported as outside of QC acceptance 

criteria. 

9.3 Laboratory Matrix Spikes (LMSs) 

LMSs may be perfonned in lieu of FMSs if FMSs have previously been performed for the sample matrix. 

Additionally, LMSs may be performed in lieu of FMSs for a sample matrix if the FMS levels were not 

appropriate for detemnining spike recoveries relative to endogenous levels of target analytes and appropriate 

SRSs. Generally, each sample location represents a different sample and sample matrix. LMSs are prepared 

for each sample and analyzed to detemnine the matrix effect on spike recovery efficiency of each target analyte 

and appropriate SRSs. LMSs should be prepared at a minimum of one level and in duplicate. LMS 

concentrations should be prepared at approximately 0.5-10 times the endogenous concentration or 

approximately 4-10 times the LOQ concentration of each target analyte. 

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Lab matrix spike recoveries should fall within ± 30% of expected values. Sample data with LMS recovery 

outside of ±30% but within ±50% of the expected value are flagged and reported as outside of QC acceptance 

criteria. Data with LMS recovery outside of ±50% of the expected value are reported as NR, where NR is 

deflned as "Not Reportable" data outside of QC acceptance criteria. 

9.4 Lab Control Sample 

Lab control spikes are prepared for each analysis batch to determine method accuracy and precision. LCSs 

should be prepared at three levels in triplicate for each target analyte and at a minimum of two levels in 

triplicate for appropriate SRSs. Low lab control spikes should be prepared at a concentration in the range of 

approximately four to ten times higher than the targeted lower LOQ; the mid lab control spikes should be 

prepared at a concentration near the mid-point of the calibration curve and the high lab control spikes at 

approximately 80% of the upper LOQ. For each target analyte and SRSs, the percent relative standard 

deviation (method precision) for each control spike level must be less than or equal to 20% and the average 

recovery (method accuracy) for each control spike level must be 80-120%. Sample data for target analytes 

outside of the laboratory control spike acceptance criteria will be handled as follows: 

If the average recovery of a spiking level falls outside method acceptance, but at least 67% (6 out of 9) of LCS 

samples are within 20% of their respective nominal value (33% of the QC samples, not all replicates at the 

same concentration, may be outside 20% of nominal value), the average recovery will be flagged as outside 

method acceptance criteria. All LCS samples will be control charted as per ETS-4-026. If the average 

recovery of one of the spiking levels exceeded the analytical method uncertainty as detemnined by ETS-12-

012, that analytical batch uncertainty will be expanded for that particular study. 

If more than 67% of the LCS samples fail to meet method acceptance criteria, the data will not be reported. 

Calibration standards consisting of mixed branched and linear isomer PFOS/PFOA are preferred. However, 

for PFOS/PFOA target analytes, if the calibration standards are comprised of predominantly linear isomers 

only, at least one level of triplicate LCSs should be prepared using PFOS/PFOA which contains a mix of linear 

and branched isomers. These LCSs will be used to demonstrate quantitative equivalency (or quantitative bias) 

of the isomeric mix when using a predominantly linear standard for calibration. The mixed linear and branched 

isomer PFOS/PFOA LCSs recoveries should fall within ± 30% of expected values. Alternatively, in lieu of 

mixed branched and linear isomer PFOS/PFOA LCSs, mixed branched and linear isomer PFOS/PFOA 

TBMSs may be applied to demonstrate method accuracy and precision. 

9.5 Field Matrix Spikes (FMSs) / Surrogate Recovery Standards (SRSs) 

FMSs are prepared for each sampling location and analyzed to determine the matrix effect and sample holding 

time on the spike recovery of each target analyte and/or appropriate SRS. Generally, each sample location 

represents a different sample and sample matrix. 

FMSs are QC samples to which known quantifies of appropriate target analytes are added to the sample bottle 

in the laboratory before the bottles are sent to the field. Typically a low and a high target analyte FMS are 

prepared for each sampling location. The sample and field duplicate sample may contain appropriate SRSs in 

lieu of target analyte low field matrix spike and target analyte high field matrix spike samples. 

Field matrix spike method acceptance criteria are recoveries within ±30% of the expected value. If FMS 

recovery (target analyte or SRS spike) is outside of ±30% of the expected value or could not be assessed 

because the FMS (target analyte) was spiked at an inappropriate level, the sample result is reported as follows: 

1. ) If target analyte FMS recovery could not be assessed because the FMS's were at an inappropriate level, 

then Laboratory Matrix Spikes (LMS) may be substituted. If LMS recoveries are within ±30% the data are 

reportable and fiagged to indicate that the FMS spikes levels were inappropriate. 

2. ) If multiple target analyte FMS's were prepared on a sample and the closest FMS level to the reported 

sample meets the ±30% acceptance criteria but additional FMS's are outside the ±30% acceptance range, the 

data are reportable and flagged to indicate that while there were failing FMS's, the uncertainty will not be 

expanded since the most appropriate spike level passed. 

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3. ) If the target analyte FMS recoveries are outside of the ±30% acceptance range but at least 30 acceptable 

historical reportable FMS sample results are available, the data may be reported but flagged with an expanded 

uncertainty and as not meeting FMS criteria. 

4. ) Sample data with FMS recovery outside of ±30% but within ±50% of the expected value are flagged and 

reported as outside of QC acceptance criteria with an expanded uncertainty. 

5. ) If FMS recovery is outside of ±50%, the sample result is reported as NR, where NR is defined as "Not 

Reportable" due to noncompliant QC results. 

The targeted fortification levels should be at least 50% of the endogenous level and less than 10 times the 

endogenous level to be used without justification to determine the statement of accuracy for analytical results. 

Note: It is possible for bottles utilized for Field Matrix Spike samples to be under-filled or over-filled during 

sample collection. Since this scenario will effect the actual concentration of the FMS sample (sun-ogate and 

internal standard concentrations will also be effected, if used), it is important that any obvious under-filling or 

over-filling of sample bottles be documented in the data package and taken into account in the FMS, ISs, or 

SRSs recovery calculations. Samples over-filled or under-filled by more than 10% will be require recalculation 

of the FMS, ISs, and SRS tme values. 

The average of the sample and the field duplicate should be used to calculate the recovery. 

10 Procedures 

10.1 Water Sample Preparation 

This method is applicable to water samples. Samples containing heavy particulate may not be suitable for 

analysis by this method. Samples containing suspended particulate should be centrifuge prior to removing a 

' sample aliquot, or filtered. 

• Thoroughly mix sample before removing an aliquot and placing in a labeled autovial. 

• Dilute sample, if necessary, with ASTM Type I water, HPLC water, other suitable water, or solvent 

(methanol). 

• Lab control spikes are prepared for each analysis batch to detennine method accuracy and precision. 

LCSs should be prepared at three levels in triplicate for each target analyte and at a minimum of two 

levels in triplicate for appropriate SRSs. Low lab control spikes should be prepared at a concentration 

in the range of approximately four to ten times higher than the targeted lower LOQ, the mid lab control 

spikes should be prepared at a concentration near the mid-point of the calibration curve and the high 

lab control spikes at approximately 80% of the upper LOQ. For IS quantitation, stable isotope internal 

standards of each target analyte or appropriate sun-ogate ISs should be spiked at the same level as the 

samples being analyzed, in all LCSs. 

• If LCSs are being prepared using synthetic groundwater, allow the LCSs samples to equilibrate for a 

minimum of 4 hours before aliquoting for analysis or diluting with solvent (methanol). 

11 Sample Analysis - LC/MS/MS 

11.1 Instrument Setup 

Note: In this example, an Applied Biosystems Sciex API 4000 (API 5000 or API 5500) Tandem Mass 

Spectrometer (LC/MS/MS) is used. Other brands/models of LC/MS/MS instruments as well as single 

quadrupole mass spectrometers (LC/MS) may be used as long as the method acceptance criteria are met. 

Brand names, suppliers, part numbers, and models are for illustrative purposes only. Equivalent perfomiance 

may be achieved using apparatus and materials other than those specified here, but demonstration of 

equivalent perfomnance that meets the requirements of this method is the responsibility of the laboratory. The 

operator must optimize and document the equipment and settings used. 

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Establish the LC/MS/MS system and operating conditions equivalent to the following: 

Mass Spec: Applied Biosystems API 4000, API 5000, or API 5500 

Ion Source: Turiao Ion Spray (ABS) 

Mode: Electrospray Negative 

Scan Type: MRM (Multiple Reaction Monitoring) 

Computer: Dell DHM 

Software: Windows 2000 or Windows XP, Analyst 1.4.2 or higher versions 

HPLC: Agilent Series 1100,1200, or 1290 

Agilent Quatemary Pump 

Agilent Vacuum Degasser 

Agilent Autosampler 

Agilent Column Oven 

Note: One or more C18 HPLC analytical columns (2.1 mm x 100 mm, 5nm or 2.1 mm x 50 mm, 5|xm) may be 

attached on-line after the purge valve and before the sample injection port to retard and separate any residue 

contaminants that may be in the mobile phase and/or HPLC system. 

HPLC Column: Betasil C18,4.6mm x 100mm, 5\im (ThennoElectron Corporation) 

Column Temperature: 35°C 

Injection Volume: 5pL 

Mobile Phase (A): 2mM Ammonium Acetate in ASTM Type I water (See 7.3) 

Mobile Phase (B): Methanol 

Table 3. Liquid Chromatography Gradient Program. 

step 

Number 

7ota/ Time 

(min) 

Flow Rate 

(ftUmin) 

Percent A 

(2 mM ammonium 

acetate) 

Percent B 

(Methanol) 

0 0 750 97.0 3.0 

1 2.0 750 97.0 3.0 

2 14.5 750 5.0 95.0 

3 15.5 750 5.0 95.0 

4 16.5 750 97.0 3.0 

5 20.0 750 97.0 3.0 

Note: Other HPLC gradients may be used as long as the method criteria and project data quality objectives are 

met. 

It may be necessary to adjust the HPLC gradient in order to optimize instrument perfomiance. Columns with 

different dimensions (e.g. 2.1mm x 30mm) and columns from different manufacturers (Keystone Betasil CI 8 

etc.) may be used. 

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Table 4 Suggested MRM Transitions for Target Analytes, Surrogates, and Internal Standards 

Analyte 

Analyte Description Mass Transition 

01 (amu) 

Mass Transition 

OS (amu) 

PFBA (C4 Acid) Target 213 169 

PFPeA (C5 Acid) Target 263 219 

PFHxA (C6 Acid) Target 313 269,119 

PFHpA (C7 Acid) Target 363 319,169 

PFOA (C8 Acid) Target 413 369,219, 169 

PFNA (C9 Acid) Target 

463 419, 169,219 

PFDA (CIO Acid) Target 513 469,269,219 

PFUnA (Oil Acid) Target 563 519,269,219 

PFDoA (012 Acid) Target 613 569, 169,319 

PFTA (CI3 Acid) Target 663 619, 369,319 

FBSA (C4 Sulfonamide) Target 298 78 

FOSA (C8 Sulfonamide) Target 498 78 

PFBS (C4 Sulfonate) Target 299 99, 80 

PFHS (C6 Sulfonate) Target 399 99, 80 

PFOS (C8 Sulfonate) Target 499 80, 99, 130 

[1,2,3,4-"C4IPFBA IS for PFBA 217 172 

[1,2,3,4,5-"CslPFPeA IS for PFPeA 268 223 

[l,2-''C2lPFHxA IS for PFHxA 315 270 

[1,2,3,4- "C4IPFHPA IS for PFHpA 367 322 

[l,2,3,4,5,6,7,8-"C8lPFOA IS for PFOA 421 376 

[ 1,2,3,4,5,6,7,8,9-"CIPFNA IS for PFNA 472 427 

[1,2,3,4,5,6-"CsJPFDA IS for PFDA 519 474 

[1,2,3,4,5,6,7-"CTlPFUnA IS for PFUnA 570 525 

[l,2-"C2lPFDoA IS for PFDoA and PFTA 615 570 

['^OJIPFBS IS for PFBS 303 84 

[l,2,3-"C3lPFHS IS for PFHS 402 80 

[1,2,3,4- "CilPFOS IS for PFOS 503 80 

[l,2,3,4,5,6,7,8-"C8lF0SA IS for FOSA 507 80 

[l,2,3,4-"C4lPF0A Surrogate (C4-C8 Acids) 417 372 

[1,2,3,4- "C4]PFOS Surrogate(Sulfonates, FOSA) 503 80 

[l,2-"C2]PFUnA Sun-ogate (C9-C13 Acids) 565 520 

Multiple transitions for monitoring the analytes is an option. The use of one daughter ion is acceptable if data 

sensitivity and selectivity is achieved and provided that retention time criteria are met to assure adequate 

specificity. While the daughter ions may be chosen at the discretion of the analyst, mass transition 99 is 

suggested for PFOS. Quantitation may be perfonned using the total ion chromatogram (TIC, or summed 

MRMs) for a given analyte. For example, the PFOA TIC would sum all three of the monitored transitions. Use 

of the suggested primary ion is recommended. Retention times may vary slightly, on a day-to-day basis, 

depending on the batch of mobile phase and the gradient, column, guard column(s) used etc. Drift in retention 

times is acceptable within an analytical run, as long as the drift continues through the entire analysis and the 

standards are interspersed throughout the analytical run. 

11.2 Calibration Curve 

Quantitation is by intemal standard or extemal standard calibration. Calibration standards may be prepared in 

ASTM Type I, HPLC water, other suitable water, or a solvent/water mixture. If intemal standard calibration 

does not meet calibration acceptance criteria, external calibration can be applied. See Table 1 for 

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Table 4 Suggested MRM Transitions for Target Analytes, Surrogates, and Internal Standards 

Analyte 

Analyte Description Mass Transition 

Ql (amu) 

Mass Transition 

Q3 (amu) 

PFBA (C4 Acid) Target 213 169 

PFPeA (C5 Acid) Target 263 219 

PFHxA (C6 Acid) Target 313 269,119 

PFHpA (C7 Acid) Target 363 319,169 

PFOA (C8 Acid) Target 413 369,219,169 

PFNA (C9 Acid) Target 

463 419, 169,219 

PFDA (CIO Acid) Target 513 469,269,219 

PFUnA (CI 1 Acid) Target 563 519,269,219 

PFDoA (CI2 Acid) Target 613 569, 169,319 

PFTA (CI3 Acid) Target 663 619, 369,319 

FBSA (C4 Sulfonamide) Target 298 78 

FOSA (C8 Sulfonamide) Target 498 78 

PFBS (C4 Sulfonate) Target 299 99, 80 

PFHS (C6 Sulfonate) Target 399 99, 80 

PFOS (C8 Sulfonate) Target 499 80, 99, 130 

[1,2,3,4-"C4IPFBA IS for PFBA 217 172 

[1,2,3,4,5-"CslPFPeA IS for PFPeA 268 223 

[l,2-"C2lPFHxA IS for PFHxA 315 270 

[1,2,3,4- ''C4IPFHPA IS for PFHpA 367 322 

[l,2,3,4,5,6,7,8-"C8lPFOA IS for PFOA 421 376 

[1,2,3,4,5,6,7,8,9-"CIPFNA IS for PFNA 472 427 

[1,2,3,4,5,6-"CfilPFDA IS for PFDA 519 474 

[1,2,3,4,5,6,7 -"ClPFUnA IS for PFUnA 570 525 

[1,2 -"C2IPFD0A IS for PFDoA and PFTA 615 570 

['*02lPFBS IS for PFBS 303 84 

[l,2,3-"C3lPFHS IS for PFHS 402 80 

[1,2,3,4- "CilPFOS IS for PFOS 503 80 

[1,2,3,4,5,6,7,8-"CslFOSA IS for FOSA 507 80 

[l,2,3,4-"C4lPFOA Sun-ogate (C4-C8 Acids) 417 372 

[1,2,3,4-"C41PF0S Sun-ogate(SuIfonates, FOSA) 503 80 

[l,2-"C2lPFUnA Surrogate (C9-C13 Acids) 565 520 

Multiple transitions for monitoring the analytes is an option. The use of one daughter ion is acceptable if data 

sensitivity and selectivity is achieved and provided that retention time criteria are met to assure adequate 

specificity. While the daughter ions may be chosen at the discretion of the analyst, mass transition 99 is 

suggested for PFOS. Quantitation may be perfonned using the total ion chromatogram (TIC, or summed 

MRMs) for a given analyte. For example, the PFOA TIC would sum all three of the monitored transitions. Use 

of the suggested primary ion is recommended. Retention times may vary slightly, on a day-to-day basis, 

depending on the batch of mobile phase and the gradient, column, guard column(s) used etc. Drift in retention 

times is acceptable within an analytical run, as long as the drift continues through the entire analysis and the 

standards are interspersed throughout the analytical run. 

11.2 Calibration Curve 

Quantitation is by internal standard or external standard calibration. Calibration standards may be prepared in 

ASTM Type I, HPLC water, other suitable water, or a solvent/water mixture. If internal standard calibration 

does not meet calibration acceptance criteria, external calibration can be applied. See Table 1 for 

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recommended application of available internal standards. Quantitation of PFOA and PFOS is by summed 

analyte-specific mass transitions. 

Analyze the standard curve prior to each set of samples. If internal standards were added to the calibration 

standards area ratios are used to generate the calibration curve. The standard curve may be plotted using a 

linear regression (y = mx + b), weighted 1/x or unweighted, or by quadratic fit (y = ax^ + bx + c), weighted 1/x or 

unweighted, using suitable software. The mathematical method used to calculate the calibration curve should 

be applied consistently throughout a study. Any change should be thoroughly documented in the raw data. 

High and/or low points may be excluded from the calibration curves to provide a better fit over the range 

appropriate to the data or because they did not meet the pre-detennined acceptance criteria. Low-level curve 

points should also be excluded if their area counts (or area ratio if quantitating by IS) are not at least twice that 

of the average area counts (or area ratio if quantitating by IS) of method and/or solvent blanks. The coefficient 

of detennination (r^) value for the calibration curve must be greater than or equal to 0.990 (or a con-elation 

coefllcient (r) of 0.995). Each point in the curve must be within ±25% of the theoretical concentration with the 

exception of the LLOQ, which may be within ±30%. Justification for exclusion of calibration curve points will be 

noted in the raw data. A minimum of 6 points will be used to construct the calibration curve. 

If the calibration curve does not meet acceptance criteria, perfonn routine maintenance or prepare a new 

standard curve (if necessary) and reanalyze. 

11.3 Continuing Calibration Verification (CCV) 

Continuing calibration verifications (CCV) are analyzed to verify the accuracy of the calibration curve. Analyze 

a mid-range calibration standard, one of the same standards used to construct the calibration curve, at a 

minimum after every tenth sample, not including solvent blanks, with a minimum of one per sample set. 

Calibration verification injections must be within ±25% to be considered acceptable. The calibration curve and 

the last passing CCV will then bracket acceptable samples. Multiple CCV levels may be used. Samples must 

be bracketed by passing CCVs or the calibration curve and a passing CCV to be reportable. 

11.4 System Suitability 

A minimum of three system suitability samples should be injected at the beginning of each analytical run, prior 

to the analysis of the calibration curve. Typically these samples are at a concentration near the mid-level of the 

calibration curve and are repeated injections from one autosampler vial. It is suggested that the system 

suitability injections have area counts or area ratios when using internal standard calibration, with a target RSD 

of <5% and a target retention time RSD of <2%. There is no defined acceptability limit on these results as the 

%RSD value is dependent on the number of MRM transitions being monitored in the LC/MS/MS run or time 

period. Ultimately, any effects on these parameters for the System Suitability samples will also be evident on 

all standards and QC samples analyzed as part of the analysis batch. Any effect of system suitability is 

incorporated within QC acceptance criteria. 

11.5 Sample Analysis and QC s 

For each analysis batch, the instrument analysis run sequence should include an initial calibration curve, 

samples, FDSs, interspersed blanks, interspersed CCVs, appropriate QCs (i.e., LCSs, LMSs, FMSs, TBMSs, 

and TBs), and a final CCV or calibration curve bracketing samples and appropriate QCs 

Inject the same volume (between 5-1 OOpL) of each standard, analytical sample and blank into the instrument 

(unless an on-instrument sample dilution is desired). 

Samples containing analytes that are quantitated above the concentration of the highest standard in the curve 

should be further diluted and reanalyzed. 

' 3M Environmental Laboratory study E08-0096 evaluated the effect on these results as a function of the number of MRMs being monitored. 

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12 Data Analysis and Calculations 

The chromatography analysis software will typically calculate the amount of target analyte in the sample 

extracts using the established calibration curve. 

Calculate the percent recovery of the LCS using the following equation: 

LCS Concentration (—) 

LCS% recovery = * 100% 

ng 

Spike Concentration (——) 

mL 

Calculate the percent recovery of the LMS using the following equation: 

LMS Concentration (-^) - Concentration of Sample (,-^) 

LMS % recovery = ^ * 100% 

Spike Concentration (-^ ) 

mL 

For samples fortified with known amounts of analyte prior to extraction, use the following equation to calculate 

the percent recovery. 

Recove - ^"^'y*® found (ng/mL) - Average analyte found in sample (ng/mL) ^ .| QQ 

Analyte added (ng/mL) 

13 Analysis Batch Method Performance Criteria 

Any method perfomnance parameters that are not achieved must be considered in the evaluation of the data. 

Nonconfonnance to any specified parameters must be described and discussed in the final report if the 

Technical Manager (non-GLP study) or Study Director (GLP study) chooses to report the data. 

If criteria listed in this method performance section are not met, maintenance may be perfonned on the system 

and samples reanalyzed, or other actions taken as appropriate. Document all actions in the raw data. 

If data are to be reported when perfomiance criteria have not been met, the data must be footnoted on tables 

and discussed in the text of the report. 

13.1 System Suitability - Analysis Batch 

A minimum of three system suitability samples should be injected at the beginning of each analytical mn. 

These samples are run prior to the calibration curve. It is suggested that the system suitability injections have 

area counts with a target RSD of ^5% and a target retention time RSD of s2%. There is no defined 

acceptability limit on these results as the %RSDs are dependent on the number of MRM transitions being 

monitored in the LC/MS/MS mn or time period. Any effect of system suitability is incorporated in the QC 

acceptance criteria. 

13.2 Calibration and Limit of Quantitation (LOQ) - Analysis Batch 

Calibration Curve: The coefficient of determination (r^) value for the calibration curve must be greater than or 

equal to 0.990 corresponding to a con-elation coefficient (r) = 0.995. Each point in the curve must be within 

±25% of the theoretical concentration with the exception of the LLOQ, which may be within ±30%. 

CCV Performance: The calibration standards that are interspersed throughout the analytical sequence are 

evaluated as continuing calibration verifications in addition to being part of the calibration curve. The accuracy 

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of each curve point must be within 25% of the theoretical value (within 30% for lowest curve point). Samples 

that are bracketed by CCVs not meeting these criteria must be reanalyzed. 

Limits of Quantitation (LOQ): The lower LOQ (LLOQ) is the lowest non-zero active standard in the 

calibration curve; the peak area of the LLOQ must be at least 2X that of the average area counts for all 

prepared procedural blank(s). By definition, the measured value of the LLOQ must be within 30% of the 

theoretical value. 

Demonstration of Specificity: Specificity is demonstrated by chromatographic retention time (within 4% of 

standard) and the mass spectral response of unique ions. 

13.3 Blanks - Method/Procedural Blanks and Trip 

Mettiod/Procedural Blanks: Multiple procedural blanks should be interspersed throughout the analysis batch 

and the analytical sequence. At a minimum, method blanks are analyzed prior to instmment calibration, prior 

to the analysis of CCV samples, after every 10 sample injections, and at the end of the analytical run. 

The mean area counts (or area ratios when using IS calibration) for each analyte must be less than 50% of the 

area count of the LOQ standard. If the area counts of the procedural blanks exceed 50% of the LOQ standard, 

then the LOQ must be raised to the first standard level that meets criteria. 

Trip Biank: A trip blank of ASTM Type I water (or lab equivalent) is prepared in a sample container in the 

laboratory and treated as a sample, including exposure to shipping, sampling site conditions, storage, 

preservation and all analytical procedures. The trip blanks results for each analyte are included with the 

reported sample results. 

13.4 Data Accuracy and Precision - Analysis Batch 

Lab Control Spikes: The average recovery at each LCS level for each target analyte and appropriate SRS 

should be within 80-120% and the percent relative standard deviation of the recoveries must be less than or 

equal to 20%. If the average recovery of a spiking level falls outside method acceptance, but at least 67% (6 

out of 9) of LCS samples are within 20% of their respective nominal value (33% of the QC samples, not all 

replicates at the same concentration, may be outside 20% of nominal value), the average recovery will be 

flagged as outside method acceptance criteria. AH LCS samples will be control charted as per ETS-12-012. If 

the average recovery of one of the spiking levels exceeded the analytical method uncertainty as detennined by 

ETS-12-012, that analytical batch uncertainty will be expanded for that particular study. The average recovery 

at each LCS level for mixed branched/linear isomer PFOA and PFOS should be within 70-130% and the 

percent relative standard deviation of the recoveries must be less than or equal to 20%. 

Field Duplicates: The relative percent difference (RPD) of duplicate samples should be less than 20% for the 

precision of sample preparation and analysis to be considered in control. Replicate samples not meeting the 

20% RPD criteria are flagged and reported as outside of QC acceptance criteria. 

Field Matrix Spikes: FMS acceptance criteria are recoveries within ±30% of the expected value for each 

target analyte and appropriate SRS. Sample data with FMS recovery outside of ±30% but within ±50% of the 

expected value are fiagged and reported as outside of QC acceptance criteria. Data with FMS recovery 

outside of ±50% of the expected value are reported as NR, where NR is defined as "Not Reportable" data 

outside of QC acceptance criteria. If FMS recovery could not be assessed because FMSs were at an 

inappropriate level, then Laboratory Matrix Spikes (LMSs) may be substituted. If LMS recoveries are within 

±30% for each target analyte and SRSs the data are reportable but flagged as not meeting the FMS method 

acceptance criteria. 

13.5 Analytical Method Uncertainty 

Analytical method uncertainty for each target analyte and SRS is detemnined with control charted historical 

analysis batch LCS data for the method and reported with each analysis batch.* Uncertainty detenninations 

' Method uncertainty based on INTERNATIONAL ANS/ISO/IED STANDARD 17025 reference (GUM, Guide to the Expression of 

Uncertainty in Measurement). Method application demonstrated in ETS-12-012, citing references: a.) EURACHEM/CITAC Guide, 

"Quantifying Uncertainty in Analytical Measurement," Second Edition; Editors: S.L.R. Ellison, M. Rosslein, and A. Williams. 

b.)Georgian, Thomas, "Estimation of Laboratory Analytical Uncertainty Using Laboratory Control Samples," Environmental Testing & 

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Bert Jeffries Landfill - February 2012 

are based on INTERNATIONAL ANS/ISO/IED STANDARD 17025 reference (GUM, Guide to the Expression 

of Uncertainty in Measurement) and described in ETS-12-012. At least thirty data points are required for 

detennining analytical method uncertainty. The method uncertainty is defined as 2x the standard deviation of 

the percent recoveries of the pooled lab control spikes. While all LCS data points are control charted, only the 

most recent fifty data points are used for detemnining the method uncertainty. 

When less than thirty LCS data points have been generated for a given analyte, the analysis batch LCSs are 

used to detennine the data uncertainty. If FMSs meet the ±30% recovery criteria at a level appropriate to the 

endogenous level, and the LCS meet the ±20% recovery criteria, then the uncertainty of the data is detemnined 

as within 100±20%. 

Analysis batch sample data with FMS recovery outside of ±30% but within ±50% of the expected value are 

flagged and reported as outside of QC acceptance criteria with expanded uncertainties. Data with FMS 

recovery outside of ±50% of the expected value are reported as NR, where NR is defined as "Not Reportable" 

data outside of QC acceptance criteria. If FMS recovery could not be assessed because FMSs were at an 

inappropriate level, then Laboratory Matrix Spikes (LMSs) may be substituted. If LMS recoveries are within 

±30% for each target analyte and appropriate SRSs the data are reportable but fiagged as not meeting the 

FMS method acceptance criteria with uncertainties of ±30%. If FMS do not meet the ±30% recovery criteria, 

and historical FMS data does not exist, the analytical uncertainty is evaluated on a sample-by-sample basis, 

the data may be reported with expanded uncertainty and are flagged. 

13.6 Quantitation of PFOA/PFOS - Analysis Batch 

Calibration standards consisting of mixed branched and linear isomer PFOS/PFOA are preferred. 

Quantitation is perfoimed by integrating the linear and branched isomers together. Altemately, the linear and 

branched isomers can be integrated separately, applying the appropriate tme value to each calibration curve 

point for each isomer. The LCS and samples are then quantitated by integrating the linear and branched 

isomers separately (requires separate analytical results files) and quantitating the resulting peak against the 

linear or branched calibration curve. The results from both integrations are then summed to produce the final 

result. Integrating the linear and branched isomers separately may be helpful for those samples where the 

linear/branched ratios do not closely match those of the reference standards. 

However, for PFOS/PFOA target analytes, if the calibration standards are comprised of predominantly linear 

isomers only the method requires the addition of LCSs of mixed branched/linear isomer PFOS/PFOA. The 

purpose of including these LCSs is to demonstrate quantitative equivalency (or quantitative bias) of the 

isomeric mix when using a predominantly linear PFOS or PFOA standard for calibration. Altematively, in lieu 

of mixed branched and linear isomer PFOS/PFOA LCSs, mixed branched and linear isomer PFOS/PFOA 

TBMSs may be applied to demonstrate method accuracy and precision. 

An altemate method of quantitation can be perfomned whereby only the linear isomer of PFOS/PFOA is 

integrated and used for generating the calibration curve. The LCS and samples are then quantitated by 

integrating the linear and branched isomers separately (requires separate analytical results files) and 

quantitating the resulting peak against the linear calibration curve. The results from both integrations are then 

summed to produce the final result. Integrating the linear and branched isomers separately reduces the oncolumn concentration for those samples that contain both linear and branched isomers of PFOA/PFOS. This 

ensures that the concentration detected is within the a range of the calibration curve that is comparable 

regardless of whether the calibration curve was generated using predominantly linear isomers of PFOS/PFOA 

or linear plus branched isomers of PFOS/PFOA. 

14 Pollution Prevention and Waste Management 

Waste generated when perfomning this method will be disposed of appropriately. The original samples will be 

archived at the 3M Environmental Laboratory in accordance with internal procedures. 

Analysis, November/December 2000. c.)Taylor, B.N. and CE. Kuyatt, NIST Technical Note 1297, 1994 Edition: "Guidelines for 

Evaluating and Expressing the Uncertainty of NIST Measurement Results."d.)Adams, T.M., "A2LA Guide for the Estimation of 

Measurement Uncertainty in Testing", July 2002. 

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Analysis of PFOA in Surface Water 

Bert Jeffries Landfill - February 2012 

15 Records 

Each data package generated for a study must include all supporting infomnation for reconstmction of the data. 

Infomnation for the data package must include, but is not limited to the following items: study or project 

number, sample and standard prep sheets/records, instmment run log (instmment batch records, instmment 

acquisition method, summary pages), instrument results files, chromatograms, calibration curves, and data 

calculations. 

16 Affected Documents 

None. 

17 Revisions 

Revision 

Number Summarv of Changes 

1 Section 1. Included the use of internal standard calibration by this method. 

Section 2. Included the use of internal standard calibration by this method. Included the 

use of a solvent/water mixture when analyzing for PFUnA, PFDoA, PFTrDA, and FOSA. 

Section 3. Added definitions for internal standard, surrogate internal standard, and 

surrogate recovery standard. 

Section 6. Removed the details regarding the instrument parameters to section 10 of the 

method. 

Section 7. Updated reference standards to include intemal standards and surrogates. 

Changed concentration levels for working standards and included the use of internal 

standards and surrogates. 

Section 8. Inserted a new section on sample bottle preparation. 

Section 9 Quality Control. This section was previously section 10 in ETS-8-044.0. Updated 

QC criteria to be consistent with method ETS-8-154.4. 

Section 10 Procedures. This section was previously section 8 (Sample Handling) in ETS-8-

044.0. Added detail regarding the preparation of LCSs. Included the use of methanol as a 

dilution solvent. 

Section 11 Sample Analysis. This section was previously section 10 in ETS-8-044.0. 

Included the details regarding the instrument parameters. 

Section 12 Data Analysis and Calculations. This section was previously section 11 in ETS8-044.0. Removed the equation for calculating the analytes concentration, indicating that 

this is done by the instrument software. 

Section 13 Method Performance. This section was previously section 12 in ETS-8-044.0. 

Updated QC criteria to be consistent with ETS-8-154.4. Added information on the 

detennination of analytical method uncertainty and quantitation of PFOA/PFOS. 

Section 14 Pollution Prevention. This section was previously section 13 in ETS-8-044.0. 

Section 15 Records. This section was previously section 14 in ETS-8-044.0. 

Section 16 Affected Documents. This section was previously section 15 in ETS-8-044.0. 

Section 17 Revisions. This section was previously section 16 in ETS-8-044.0. 

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